water treatment method, water source treatment method and aqueous water treatment composition with a

专利摘要:
use of peracetic acid / hydrogen peroxide and peroxide reducing agents for the treatment of drilling fluids, fractionation fluids. recirculation water and waste water. methods for employing peracid compositions with decreased hydrogen peroxide concentration for various water treatments are disclosed including operations in oil and gas fields and / or other aseptic treatments. in many ways, peracetic acid is the preferred peracid and is treated with a peroxide reducing agent to substantially reduce the hydrogen peroxide content. methods for employing treated peracid compositions in the treatment of drilling fluids, fracturing fluids, recirculation waters and wastewater are also revealed to improve the condition of the water, reducing the oxidation damage associated with hydrogen peroxide and / or reducing infestation by bacteria.
公开号:BR112014020748B1
申请号:R112014020748-8
申请日:2013-03-13
公开日:2021-02-23
发明作者:Victor Keasler；Renato De Paula；Junzhong Li；David D. Mcsherry；Brandon Herdt；Richard Staub；Robert J. Ryther
申请人:Ecolab Usa Inc.；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The present disclosure relates to percarboxylic acid compositions and methods for using peracid compositions with decreased concentrations of hydrogen peroxide for various water treatments, including oil and gas field operations and / or other asepsis treatments. . The present invention also relates to fracturing water compositions and gel compositions comprising compositions based on stable percarboxylic acid and their use in oil and gas field operations. In many ways, peracetic acid is the preferred peracid and is treated with a peroxide reducing enzyme, such as catalase, or a peroxide reducing agent, such as a metal or a potent oxidizer, to substantially reduce the peroxide content of hydrogen. The treatment methods are particularly suitable for the treatment of drilling fluids, fractionation fluids, recirculating water and / or waste water to improve the condition of the water, reducing the oxidative damage associated with hydrogen peroxide and / or reducing infestation of bacteria. BACKGROUND OF THE INVENTION
[002] Peroxycarboxylic acids (also referred to as peracids), as well as mixed peroxycarboxylic acid systems are known for use as antimicrobial agents and bleaching agents in a variety of industries. Peracetic acid or peroxyacetic acid (PAA or POAA) (dynamic equilibrium mixture of POAA / PAA, H2O2, H2O and AA) have been used in the food and beverage industries as fast-acting, "green" antimicrobials. These products demonstrate beneficial properties for oxidizing solids and improve water quality. In addition, compared to other commercially available biocides, the use of peracetic acid results in a low environmental impact, due in part to its decomposition into innocuous components (eg acetic acid (AA), oxygen, CO2 and H2O). See, for example, US Patent No. 8,226,939, entitled "Antimicrobial Peracid Compositions with Selected Catalase Enzymes and Methods of Use in Aseptic Packaging" which is incorporated by reference in its entirety.
[003] Peracids have also been used in certain water treatment applications. However, these have been very limited in the area of commercial well drilling operations. See, for example, US Patent Publication number 2010/0160449, entitled "Peracetic Acid Oil-Field Biocide and Method", and Patent number 7,156,178, which are incorporated by reference in their entirety. However, certain water treatment applications have difficulties in using the perished during various stages of oil and gas production methods, including, for example, microbial efficacy and compatibility issues. For example, despite its rapid action and environmentally friendly properties, the use of peracids, including peracetic acid, has a number of limitations for use in water treatment methods. High doses of peracid can increase corrosion rates in conduits and equipment due, in part, to the presence of hydrogen peroxide (H2O2). In addition, peracids / H2O2 can interfere with the activity of the functional agents necessary for water treatment methods in the recovery of oil and gas, including friction reducers and thickeners, which are often critical to the fractionation process. In addition, peracids and hydrogen peroxide are prone to tempering common, naturally occurring chemicals which can severely limit their usefulness.
[004] There is still a need for improved water treatment methods. For example, from a microbiology perspective, mitigation of microorganisms is essential to minimize environmental concerns with waste and avoid contamination of systems, such as microbiologically influenced corrosion (MIC) and / or acidification of wells or reservoirs. . As a result, before the drilling and fractionation steps, the water is treated to restrict the introduction of microbes into the well or reservoir. This also acts to prevent microbes from having a negative effect on the integrity of fluids. In addition, prior to disposal, the recirculation water is treated to comply with the environmental restrictions stipulated by Organs regulatory agencies.
[005] Thus, it is an objective of the invention to replace conventional oxidizing biocides for water treatment, such as, typical equilibrium peracetic acid, hypochlorous acid or hypochlorite and / or chlorine dioxide compositions.
[006] Yet another objective of the invention is to develop methods for the treatment of water in the recovery of oil and gas that provide effective antimicrobial efficacy, without any harmful interaction with functional agents, including, for example, friction reducers and viscosity enhancers .
[007] Another objective of the invention is to develop compositions and methods for the use of atypical peracids through distillation, perhydrolysis of acetyl donors, and preferably, the use of peroxide reducing agents, such as a metal or a powerful oxidizer, to improve the stability of peracids and peracid compositions and in most cases, the peracid's antimicrobial efficacy compared to the use of conventional equilibrium peracids alone.
[008] An additional objective of the invention is to develop methods of using peracids for the treatment of water used in drilling and / or fractionation, as well as the treatment of water that is expected to be discarded resulting in cleaner water with low numbers of microorganisms.
[009] Yet another object of the invention are compositions and methods for the use of peracids, namely peracetic acid, with a peroxide reducing agent, such as a metal or potent oxidizer, or a peroxide reducing enzyme, such as a catalase enzyme, to reduce H2O2 in order to minimize the negative effects of H2O2.
[010] Still in an additional aspect, the compositions and methods of the invention are used to minimize and / or eliminate the negative effects of UV (for example, sunlight), in the treatment of water used in drilling and / or fractionation that employs enzymes peroxide reducing agents.
[011] Other objectives, advantages and characteristics of the present invention will become evident from the following specification, together with the accompanying drawings. BRIEF SUMMARY OF THE INVENTION
[012] In one aspect, the present invention provides a method of treating water comprising: (a) treating a percarboxylic acid composition with a peroxide reducing agent to generate an antimicrobial composition; (b) providing an antimicrobial composition to a water source that needs treatment to form a treated water source, wherein the treated water source comprises (i) from about 1,000 ppm inorganic peroxide reducing agent or up to about 1,000 ppm peroxide reducing enzyme, (ii) from about 0% by weight to about 1% by weight of hydrogen peroxide; (iii) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 carboxylic acid; and (iv) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 percarboxylic acid, where the ratio of hydrogen peroxide to peracid is about 0: 100 to about 1:10 by weight; and (c) directing the source of treated water to the underground environment or discarding the source of treated water with a minimized environmental impact.
[013] In a further aspect, the present invention provides a method of treating a water source comprising: adding a percarboxylic acid and peroxide reducing agent to the water source to form a source of water treated with a hydrogen peroxide to peracid ratio of about 0: 100 to about 1:10 by weight, wherein said antimicrobial composition in a solution for use with said source of treated water comprises (i) less than about 1,000 ppm of an inorganic peroxide reducing agent or less than about 1,000 ppm of peroxide reducing enzyme, (ii) from about 0% by weight to about 1% by weight of hydrogen peroxide; (iii) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 carboxylic acid; and (iv) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 percarboxylic acid. In an additional aspect, the source of treated water reduces corrosion caused by hydrogen peroxide and reduces corrosion caused by microbes, so the antimicrobial composition does not interfere with friction reducers, viscosity enhancers, other functional ingredients found in the source of water or its combinations.
[014] In a further aspect, the present invention provides an aqueous composition of water treatment with antimicrobial activity, comprising: (a) a source of water derived from production; (b) from about 1 ppm to about 1,000 ppm of a peroxide reducing enzyme; (c) from about 0% by weight to about 1% by weight of hydrogen peroxide; (d) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 carboxylic acid; and (e) from about 0.0001% by weight to about 10.0% by weight of a percarboxylic acid C1-C22, wherein the aqueous water treatment composition does not interfere with the friction reducers , viscosity enhancers, other functional ingredients found in the water source or combinations thereof, and in which the ratio of hydrogen peroxide to percarboxylic acid is from about 0: 100 to about 1:10 by weight.
[015] In a further aspect, the present invention provides an aqueous composition of water treatment with antimicrobial activity, comprising: (a) a source of water derived from production; (b) from about 0% by weight to about 1% by weight of hydrogen peroxide; and (c) from about 0.0001% by weight to about 20.0% by weight of a single or mixed percarboxylic acid, in which the aqueous water treatment composition does not interfere with the friction reducers, viscosity enhancers , other functional ingredients found in the water source or combinations thereof, and in which the ratio of hydrogen peroxide to percarboxylic acid is from about 0: 100 to about 1:10 by weight.
[016] In one aspect, the present invention provides a method of treating water comprising: (a) treating a percarboxylic acid composition with a peroxide reducing agent to generate an antimicrobial composition; (b) supplying the antimicrobial composition to a water source in need of treatment to form a treated water source, wherein the antimicrobial composition and / or the treated water source further comprises a UV blocking agent, and where the source treated water comprises (i) up to about 1,000 ppm of peroxide reducing enzyme, (ii) from about 0% by weight to about 1% by weight of hydrogen peroxide; (iii) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 carboxylic acid; and (iv) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 percarboxylic acid, wherein the ratio of hydrogen peroxide to peracid is from about 0: 100 to about 1:10 by weight; and (c) directing the treated water source in an underground environment or eliminating the treated water source having a minimized environmental impact.
[017] In another aspect, the present invention provides a method of treating a water source comprising: adding a percarboxylic acid and peroxide reducing enzyme to the water source to form a proportionately treated water source of hydrogen peroxide for peracid of about 0: 100 to about 1:10 by weight, wherein said antimicrobial composition in a solution for use with said source of treated water comprises (i) less than about 1,000 ppm of a catalase enzyme, (ii) from about 0% by weight to about 1% by weight of hydrogen peroxide; (iii) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 carboxylic acid; (iv) from about 0.0001% by weight to about 10.0% by weight of a C1-C22 percarboxylic acid; and (v) from about 0.00001% by weight and about 5% by weight of said UV blocking agent. In an additional aspect, the treated water source reduces corrosion caused by hydrogen peroxide and reduces induced microbial corrosion, and in which the antimicrobial composition does not interfere with friction reducers, viscosity enhancers, other functional ingredients found in the water source or their combinations.
[018] Although various embodiments are described, still other embodiments of the present invention will be apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Therefore, figures and detailed description should be considered as illustrative and not restrictive in nature. BRIEF DESCRIPTION OF THE FIGURES
[019] Figures 1-2 illustrate a modality of the invention where the use of peptide with catalase decreases the corrosion rates of carbon steel.
[020] Figure 3 shows the average log reduction generated after 2.5 minutes and 5 minutes of exposure time to various concentrations of POAA necessary to achieve 20 ppm residual POAA within various mixtures of fractionation water.
[021] Figure 4 shows the biocidal efficacy of the PAA / H2O2 and PAA / H2O2 / catalase compositions after a period of 10 minutes of contact according to an embodiment of the invention.
[022] Figure 5 shows the biocidal efficacy of the PAA / H2O2 and PAA / H2O2 / catalase compositions after a period of 60 minutes of contact according to an embodiment of the invention.
[023] Figure 6 shows the average log reduction generated after a 2.5 minute exposure time to various concentrations of POAA to reach 20 ppm residual POAA within fractionation water mixtures.
[024] Figure 7 shows the average log reduction generated after an exposure time of 2.5 minutes to 30 ppm or 40 ppm of EnviroSan POAA with or without catalase in different mixtures of fractionation water according to the modalities of the invention.
[025] Figure 8 shows the POAA titration data in solutions treated with catalase and (untreated) of the test substance EnviroSan according to the modalities of the invention.
[026] Figure 9 shows the average log reduction generated after an exposure time of 2.5 minutes at 30 ppm of EnviroSan POAA with or without catalase pretreatment in different fractionation water mixtures according to the invention.
[027] Figure 10 shows the average log reduction generated after an exposure time of 5 minutes at 30 ppm of EnviroSan POAA with or without catalase pretreatment in different fractionation water mixtures according to the invention.
[028] Figure 11 shows the average log reduction generated after an exposure time of 5 minutes at 30 ppm POAA EnviroSan with or without catalase in different mixtures of fractionation water that were pretreated with 500 ppm of the EnviroSan product more than 1 hour before microbiological tests.
[029] Figure 12 shows the log survivors present 2.5, 5 and 60 minutes after adding a culture of P. aeruginosa to different mixtures of fractionation water according to the modalities of the invention.
[030] Figure 13 shows the average log reduction generated after an exposure time of 2.5 and 5 minutes at 30 ppm PAA with catalase against rising PAA levels alone in various fractionation water mixtures.
[031] Figure 14 shows the impact of the ratio of POAA to H2O2 on the stability of POAA according to the modalities of the invention.
[032] Figures 15-16 illustrate the impact of the addition of catalase on the stability of the peracid in the treatment waters according to the invention.
[033] Figure 17 shows the synergy of the antimicrobial efficacy of peracid combined with mixtures of water sources according to the modalities of the invention.
[034] Figure 18 shows the compatibility of the peracid and catalase compositions for use in gel formation for gel fractionation fluids according to the modalities of the invention.
[035] Figure 19 shows the compatibility of the peracid and catalase compositions as a result of combining processes for producing reduced peroxide peroxide compositions according to the modalities of the invention.
[036] Figure 20 shows the impact on the stability of the peracid composition in various sources of contaminated water pretreated according to the modalities of the invention.
[037] Figure 21 shows the differences in stability of the composition of POAA according to modalities of the invention.
[038] Figure 22 shows the difference in the decomposition of POAA within a peracid composition treated with an inorganic metal peroxide reducing agent, where the peracid compositions have different concentrations of hydrogen peroxide.
[039] Figure 23 shows the rate of loss of concentration of POAA in the presence of a platinum peroxide reducing agent.
[040] Figure 24 shows the decomposition of the AOPA compositions treated with a platinum peroxide reducing agent (with / without a catalytic enzyme peroxide reducing agent) according to the modalities of the invention.
[041] Figure 25 shows the decomposition of hydrogen peroxide and POAA in peracid compositions treated with various metal catalysts (for example, peroxide reducing agents) according to the modalities of the invention.
[042] Figures 26-27 illustrate loss of POAA (figure 26) and loss of hydrogen peroxide (figure 27) as a function of time, in the presence of a CoMo peroxide reducing agent according to the modalities of the invention .
[043] Figures 28-29 illustrate loss of POAA (figure 28) and loss of hydrogen peroxide (figure 29) as a function of time, in the presence of a NiW peroxide reducing agent according to the modalities of the invention.
[044] Figures 30-33 illustrate loss of POAA (figures 30, 32, 33) and loss of hydrogen peroxide (figures 31-33) as a function of time, in the presence of a NiMo peroxide reducing agent according to with modalities of the invention.
[045] Figures 34-37 illustrate loss of POAA (figures 34, 36, 37) and loss of hydrogen peroxide (figures 35-37), as a function of time, in the presence of a Mo peroxide reducing agent according to the modalities of the invention.
[046] Various embodiments of the present invention will be described in detail with reference to the figures, in which similar reference numbers represent similar parts through different views. The reference to various modalities does not limit the scope of the invention. The figures represented in this document are not limitations to the various modalities according to the invention and are presented for exemplary illustration of the invention. DETAILED DESCRIPTION OF THE INVENTION
[047] The present description refers to peracid compositions with substantially low or none hydrogen peroxide content for use in water treatments. In particular, peroxycarboxylic acids treated with a peroxide reducing agent, such as a metal or a powerful oxidizer, are provided to reduce and / or eliminate hydrogen peroxide from peroxycarboxylic acid, as well as methods for treating various sources of water with the same and use in the recovery of oil and gas.
[048] The methods and compositions described in this document have several advantages over conventional peracid compositions used for water treatment and / or other antimicrobial treatments. For example, peracid compositions treated with a peroxide reducing agent (or other means of substantially reducing the hydrogen peroxide content), according to the methods described herein, have significantly lower levels of oxidizing hydrogen peroxide. Beneficially, the reduction and / or elimination of hydrogen peroxide compared to untreated peracid compositions provides greater antimicrobial efficacy, eliminates harmful interaction with friction reducers and other functional ingredients used in water treatments, and / or reduces the impact environmental impact of treated water when disposed of. In addition, the treated peracid compositions greatly reduced the gasification potential and thus continue to prevent acidification of the well and reservoir, as well as preventing microbiologically influenced corrosion. These and other benefits of the present invention are described in the present document.
[049] The embodiments of the present invention are not limited to specific peroxycarboxylic acid compositions (preferably treated with a peroxide reducing agent, such as a metal or strong oxidizing agents to reduce hydrogen peroxide) and the methods for using them , which may vary and are understood by those skilled in the art. It should also be understood that all the terminology used in this document is intended to describe only particular modalities, and is not intended to be limiting in any way or scope. For example, all units, prefixes and symbols can be indicated, in their accepted SI form. Numerical ranges cited in the specification are inclusive of the numbers that define the range and include each integer within the defined range.
[050] It should be noted that, as used in this specification and the accompanying king-vindications, the singular forms "one," "one," and "o, a" include references to the plural unless the context clearly indicates the contrary. Thus, for example, the reference to a composition containing "a compound" includes a composition with two or more compounds. It should also be noted that the term "or" is generally used in its sense including "and / or" unless the context clearly indicates otherwise.
[051] Thus, so that the present invention can be more easily understood, certain terms are defined first. Unless otherwise stated, all technical and scientific terms used in this document have the same meaning as that normally understood by one skilled in the art to which the modalities of the invention refer. Many methods and materials similar, modified, or equivalent to those described in this document can be used in the practice of the modalities of the present invention, without undue experimentation, the preferred materials and methods being described in this document. When describing and claiming the modalities of the present invention, the following terminology will be used in accordance with the definitions set out below.
[052] Throughout this disclosure, the various aspects of the present invention are presented in the form of a banner. It should be understood that the description in strip format is for convenience and brevity only and should not be interpreted as an inflexible limitation on the scope of the invention. Therefore, the description of a range should be considered as having specifically disclosed all possible sub-ranges or ranges, as well as the individual numerical values within that range. For example, the description of a series, such as 1 to 6 should be considered to have specifically disclosed sub-ranges, such as 1-3, 14, 1-5, 2-4, 2-6, 3-6, etc. ., as well as the individual numbers within this range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the width of the range.
[053] As used in this document, the term "about" refers to variation in the numerical quantity that can occur, for example, through liquid handling procedures used to obtain concentrates or solutions for use in the real world ; for inadvertent error in these procedures; through differences in the manufacture, origin, or purity of the ingredients used to obtain the compositions or perform the methods; and the like. The term "about" also encompasses values that differ due to the different equilibrium conditions for the resulting composition from a particular initial mixture. Whether or not modified by the term "about", the claims include equivalent amounts.
[054] The term "cleaning", as used in this document, means carrying out or assisting in the removal of dirt, whitening, the reduction of the microbial population, 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 significantly by more than is obtained by washing with water. Larger reductions in the microbial population provide greater levels of protection.
[055] As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components, ingredients or the like, but only if the steps, components and / or additional ingredients do not materially alter the basic and new features of the claimed methods and compositions. It is understood that the aspects and modalities of the invention described in this document include "consisting of" and / or "consisting essentially" of the aspects and modalities.
[056] As used herein, the term "disinfectant" refers to an agent that kills all vegetative cells, including most recognized pathogenic microorganisms, using the procedure described in the AOAC Use Dilution Methods, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 955.14 and applicable sections, 15th edition, 1990 (EPA Guideline 91-2). As used in this document, the term "high-level disinfection" or "high-level disinfectant" refers to a compound or composition that kills substantially all organisms except high levels of bacterial spores and is carried out with a bleached chemical germicide for marketing as a sterilizer by the Food and Drug Administration. As used herein, the term "intermediate level disinfection" or "intermediate level disinfectant" refers to a compound or composition that kills mycobacteria, most viruses and bacteria with a chemical germicide registered as tuberculocidal by Environmental Protection Agency (EPA). As used herein, the term "low level disinfection" or "low level of disinfection" refers to a compound or composition that kills some viruses and bacteria with a chemical germicide registered as a hospital disinfectant by the EPA.
[057] As used herein, the term "exempt", "none", "substantially none" or "substantially exempt" refers to a composition, mixture or ingredient that does not contain a particular compound or to which a specific compound or compound containing the specific compound has not been added. According to the invention, the reduction and / or elimination of hydrogen peroxide according to the modalities provides compositions free of hydrogen peroxide or substantially free. In the event that the particular compound is present through contamination and / or the use of a minimal amount of a composition, mixture, or ingredients, the amount of the compound may 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.
[058] As used herein, the term "microorganism" refers to any non-cellular or single-celled organism (including colonial). Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyan bacteria), spores, lichens, fungi, protozoa, viruses, viroids, viruses, phages, and some algae. As used in this document, the term "microbe" is synonymous with a microorganism.
[059] As used herein, the term "mixed" or "mixture", when used, referring to "percarboxylic acid composition," "percarboxylic acids," "peroxycarboxylic acid composition" or "peroxycarboxylic acids" refers to a composition or mixture, including more than one percarboxylic or peroxycarboxylic acid.
[060] As used in this document, the term "sanitizer" refers to an agent that reduces the number of contaminating bacteria to safety levels, as assessed by public health requirements. In one embodiment, sanitizers for use in the present invention will provide at least a 99.999% reduction (5-log reduction). These reductions can be assessed through a procedure provided for in the Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 960.09 and applicable sections, 15th Edition 1990 (EPA Guideline 91-2) . According to this reference, a sanitizer must provide a 99.999% reduction (5-log reduction) within 30 seconds, at room temperature, 25 + -2 ° C, against various test organisms.
[061] Differentiation of "static" or "static" antimicrobial activity, definitions that describe the degree of effectiveness, and official laboratory protocols for measuring that effectiveness are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can affect two types of damage to microbial cells. The first is a lethal and irreversible action, resulting in the complete destruction of microbial cells or incapacitation. The second type of cellular damage is reversible, so that, if the organism becomes free of the agent, it can multiply again. The first is called microbicide and the last, microbiostat. A sanitizer and a disinfectant are, by definition, the agents that provide antimicrobial or microbicidal activity. In contrast, a preservative is generally described as an inhibitor or microbiostatic composition.
[062] As used herein, the term "water" for the treatment according to the invention includes a variety of sources, such as drinking water, reservoir water, sea water, salt water or brine source, brackish water, recycled water or the like. Water is also understood to optionally include both sources of drinking and recycled water (for example, "waste water"), as well as any combination of water for the treatment according to the invention.
[063] As used herein, "percent by weight", "percent by weight", "percent by weight" and its variations refer to the concentration of a substance, such as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used herein, "percent", "%", and the like has the same meaning as "percentage by weight", "% by weight", etc. Modalities of the Invention
[064] The invention relates generally to the use of peroxide reducing agents, such as, a metal or a potent oxidizer, for use with the peracid compositions. The invention uses peroxide-reducing agents from peracid compositions for use in water treatments in the area of oil and gas recovery. The invention further relates to the use of additional methods to reduce and / or eliminate hydrogen peroxide from peracids to provide benefits similar to those of a peracid composition. The additional methods, which produce a very low hydrogen peroxide to peracid ratio are equally advantageous and suitable for use according to the invention, including those disclosed in US Provisional Patent Application Serial Number 61 / 710,631, filed October 5 of 2012 and entitled "Stable Proxycarboxylic Acid Compositions and Uses Thereof" and the serial number conversion order ..., which are incorporated into this document as a reference in its entirety. These may include, for example, equilibrium peracid compositions distilled to recover a mixture of hydrogen peroxide and very low peroxide, other catalysts for the decomposition of hydrogen peroxide (for example, biomimetic complexes) and / or the use of perhydrolysis of peracid precursors, such as esters (e.g., triacetin) and amides with separable alkyl groups with C1-C8 carbon chain lengths, to obtain peracids with very low hydrogen peroxide content. Compositions
[065] The compositions of the invention may comprise, consist of and / or consist essentially of a peracid composition with a low hydrogen peroxide to peracid ratio. In one aspect, the peracid composition has a hydrogen peroxide to peracid ratio in a concentrated composition of about 0: 100 to about 1:10, preferably about 0.5: 100 and about 1: 100 , and more preferably from about 1: 100 to 1:10. The compositions of the invention may comprise, consist of and / or consist essentially of a peracid composition and a peroxide reducing agent used to obtain a resulting peracid composition having a low ratio of hydrogen peroxide to peracid. In chemical equilibria, there is a dynamic balance between peracids, respective carboxylic acids, hydrogen peroxide and water, in a composition. For example, a peracetic acid composition further includes acetic acid, hydrogen peroxide and water in the aqueous commercial formulation. Thus, the compositions of the invention may further comprise, consist of and / or consist essentially of a composition of peracid, carboxylic acid, hydrogen peroxide, and a peroxide reducing agent. In other respects, additional functional ingredients, such as a friction reducer, corrosion inhibitor, viscosity painter and / or an additional antimicrobial agent are employed in the compositions. In other respects, no additional functional ingredients are used in the compositions. Peroxide Reducing Enzyme
[066] In one aspect of the invention, a peroxide reducing agent is used to reduce and / or eliminate the concentration of hydrogen peroxide in an antimicrobial peracid composition. In some respects, the peroxide reducing agent is a peroxide reducing enzyme. 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. Beneficially, the reduction and / or elimination of hydrogen peroxide (potent oxidizer) results in other additives for a water treatment source (for example, water source), not being degraded or made incompatible. Various additives used to improve or modify the characteristics of aqueous fluids used in well drilling, recovery and production applications are at risk of degradation due to the effects of hydrogen peroxide oxidation. These may include, for example, friction reducers, fouling inhibitors and viscosity enhancers used in drilling commercial wells, finishing and stimulating wells or production applications.
[067] Various sources of catalase enzymes (or other enzyme peroxide reducing agents) can be employed according to the invention, including: animal sources, such as bovine catalase isolated from bovine livers; fungal catalases isolated from fungi, including Penicillium chrysogenum, Penicillium notatum, and Aspergillus niger; vegetable sources; bacterial sources, such as Staphylcocus 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.
[068] Catalases (or other enzyme peroxide reducing agents) are commercially available in various forms, including liquid and dry spray form. Commercially available catalase includes both the active enzyme as well as additional ingredients to improve the stability of the enzyme. Some examples of 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. Additional description of suitable catalase enzymes is incorporated into this document by reference in its all from US Patent Publication number 2012/0321510 and US Patent numbers 8,241,624, 8,231,917 and 8,226,939, which are hereby incorporated by reference in their entirety.
[069] In one aspect of the invention, catalase enzymes (or other peroxide reducing enzyme agents) have a high ability to decompose hydrogen peroxide. In some respects, the catalase enzymes (or other peroxide reducing enzyme agents) used in the present invention include enzymes, with a high ability to decompose hydrogen peroxide. In some embodiments, the enzyme is able to degrade at least about 500 ppm of hydrogen peroxide into a peracid composition in 15 minutes. In other respects, the enzymes used in the present invention include catalase enzymes (or other peroxide reducing enzyme agents), with a high ability to decompose hydrogen peroxide at low concentrations. In some embodiments, the concentration of enzyme required to degrade 500 ppm of hydrogen peroxide in a peracid composition in 15 minutes is less than 200 ppm, less than 100 ppm, and less than 50 ppm.L
[070] Beneficially, the reduction or elimination of hydrogen peroxide from oxidizing compositions alleviates the inconveniences caused by various oxidizing agents. In particular, the use of catalase (or other enzyme peroxide reducing agents) with the peracid compositions provides improved antimicrobial benefits without causing the damage associated with conventional oxidizing agents, (for example, peracetic acid, hypochlorous acid or hypochlorite, and / or chlorine dioxide), such as corrosion.
[071] Peroxidase enzymes (or other enzyme peroxide reducing agents) can also be used to decompose hydrogen peroxide from a peracid composition. Although peroxidase enzymes work mainly to allow oxidation of hydrogen peroxide substrates, they are also suitable for effectively reducing the proportions of hydrogen peroxide to peracid in the compositions. Various sources of peroxidase enzymes (or other enzyme peroxide reducing agents) can be employed according to the invention, including, for example, animal, fungal, peroxidase sources and genetic variations and their modifications. Peroxidases are commercially available in various forms, including liquid and dry spray forms. Commercially available peroxidases include both the active enzyme, as well as additional ingredients to improve the stability of the enzyme. In some embodiments, the peroxide reducing enzyme is able to degrade at least about 50% of the initial hydrogen peroxide concentration in a peracid composition. Preferably, the enzyme is supplied in sufficient quantity 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 concentration of hydrogen peroxide in a peracid composition by more than 90%. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[072] In one aspect of the invention, peroxide reducing enzymes are suitable for use and have a tolerance over a wide range of temperatures, including temperature ranges in water treatment applications, which can vary from about 0 -180 ° C. Although temperature and other ambient conditions may affect the stability of the enzymes, the appropriate peroxide reducing 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, and more preferably for at least about 24 hours. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[073] In another aspect of the invention, the peroxide reducing enzymes described in this document have a tolerance for pH ranges that can be found in water treatment applications. Levels of acetic acid (or other carboxylic acid) in a water treatment application can vary widely in parts per million (ppm) of acetic acid or another carboxylic acid. The solutions will have a corresponding range of pH range from more than 0 to about 10. An appropriate peroxide reducing enzyme will maintain at least about 50% of its activity in such carboxylic or acetic acid solutions over a period about 10 minutes, preferably for at least about 1 hour, and more preferably for at least about 24 hours. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[074] In one aspect of the invention, a peroxide reducing enzyme is present in a solution for use in the treatment of water and the peracid composition in sufficient quantities to reduce the concentration of hydrogen peroxide from the peracid composition to sufficiently reduced or eliminated concentration within at least a few hours, preferably within less than 10 hours, preferably within less than 5 hours, preferably within less than 4 hours, and even more preferably within less than 1 hour . In one aspect of the invention, a peroxide reducing enzyme is present in a solution for use in the treatment of water and the peracid composition in amounts sufficient to reduce the concentration of hydrogen peroxide from the peracid composition by at least 50 % at about 10 minutes, preferably within about 5 minutes, preferably within about 2 to 5 minutes, more preferably within about 1 minute. The concentration ranges of the enzymes can vary depending on the time period in which 50% of the hydrogen peroxide from the peracid composition is removed.
[075] In certain aspects of the present invention, a peroxide reducing enzyme is present in a solution composition for use, including the source of water to be treated in amounts of at least about 0.5 ppm, preferably between about 0.5 ppm and about 1,000 ppm, preferably between about 0.5 ppm and about 500 ppm, preferably between about 0.5 ppm and 100 ppm, and most preferably between about 1 ppm and about 100 ppm. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[076] The enzymes used can be free-floating in the composition of the solution to use, which means that the enzyme is part of the composition, without being attached to a surface.
[077] Alternatively, the enzymes can be immobilized on a surface that is in fluid communication with the composition of the use solution in a way that allows the enzyme to interact and decompose hydrogen peroxide from the peracid compositions. The immobilized enzyme may be more stable than the unbound, soluble enzyme. The immobilized enzyme also shows an increase in thermal and pH stability, which may be due to the protection that the substrate provides against sudden thermal variations and pH. An immobilized enzyme also has the advantage of being able to be easily removed from the rest of the composition. An immobilized enzyme can include a soluble enzyme that is bound to a substrate. Examples of substrates may include polyurethane foams, polyacrylamide gels, maleic anhydride polyethylene gels, maleic anhydride polystyrene gels, cellulose, nitrocellulose, silastic resins, porous glass, macroporous glass membranes, glass microspheres, activated clay, zeolites, alumina, silica, silicate and other inorganic and organic substrates. The enzyme can be attached to the substrate in several forms, including covalent support bonding, crosslinking, physical adsorption, ionic bonding and trapping.
[078] In one aspect, the peroxide reducing enzyme is added to a peracid usage solution instead of a concentrated peracid composition. Without being limited to a mechanism of action, the use of an enzyme peroxide reducing agent is preferably added to a non-concentrated peracid composition in order to maintain the viability and capacity of the peroxide reducing agent. For example, in one aspect, a concentrated peracid composition (for example, about 10% by weight of peracid or more, or about 15% by weight of peracid or higher) is diluted to a water source and subsequently enzyme peroxide reducing agent is added. In one aspect, the diluted water source may be the source of water that needs treatment according to the invention. In another aspect, the water source can be diluted in a solution using the peracid composition (or the less concentrated peracid composition) for subsequent dosing at the water source, which requires treatment according to the invention. Inorganic Peroxide Reducing Agent
[079] In one aspect of the invention, a peroxide reducing agent is used to reduce and / or eliminate the concentration of hydrogen peroxide in an antimicrobial peracid composition. In some respects, the peroxide reducing agent is an inorganic peroxide reducing agent. In one aspect of the invention, the agent is a metal and / or a powerful oxidizing agent. The metal catalyzes the decomposition of hydrogen peroxide into water and oxygen. In addition, the metal catalyzes the decomposition of the peracid in equilibrium. Without being limited to a specific mechanism of the invention, the decomposition of hydrogen peroxide and peroxide from an equilibrium peroxide composition catalyzed by the peroxide reducing agent beneficially results in a reduction of peroxide in an accelerated oxidation reaction causing an efficacy increased or elevated antimicrobial.
[080] Beneficially, the reduction and / or elimination of hydrogen peroxide (for example, an oxidizer) results in other additives for a water treatment source (for example, water source), not being degraded or made incompatible. This is important, since several additives used to improve and / or modify the characteristics of aqueous fluids used in production well drilling applications, recovery and / or production applications are at risk of degradation due to oxidation effects of peroxide. hydrogen. These may include, for example, friction reducers, scale inhibitors and viscosity enhancers used in the drilling of commercial wells, as well as production, completion or production applications. According to one aspect of the invention, the significant reduction of hydrogen peroxide from a peracid composition reduces or eliminates these compatibility and / or degradation issues.
[081] In one aspect, the peroxide reducing agent is a metal, combination of metals and / or a metal compound. Examples of metals suitable for use as peroxide reducing agents (for example, decomposition agents) include heavy metals. In another aspect, metal oxides can be used according to the invention. For example, suitable metals include platinum, palladium, bismuth, tin, copper, manganese, iron, tungsten, zirconium, rhodium, cobalt, molybdenum, nickel, iron, copper and / or manganese. In a preferred aspect, metals include platinum, tungsten, zirconium, ruthenium, cobalt, molybdenum, nickel, iron, copper and / or manganese. In another preferred aspect of use in field operations for production well drilling applications, in recovery and / or production applications, metals include iron, copper and / or manganese. In other aspects of the invention, a combination of metals can be used as the peroxide reducing agent.
[082] In one aspect, the peroxide reducing agent is a potent oxidizer. Without being limited to a particular mechanism of action of the compositions and / or methods of the invention, the oxidant has a greater oxidation potential than hydrogen peroxide, beneficially allowing the decomposition of oxidizing hydrogen peroxide. Examples of potent oxidants suitable for use as peroxide reducing agents include halide anions, halide salts and / or halide sources, including, for example, bromide and / or bromine, iodide and / or iodine, chlorine and / or chloride, fluorine and / or fluoride, etc. In a particular aspect, the peroxide reducing agent is a source of chlorine, including, for example, sodium hypochlorite or hypochlorite, chlorine dioxide, or the like.
[083] In another aspect of the invention, the agent is not sensitive to UV rays. In another aspect of the invention, metals and / or potent oxidizing agents have a high capacity to decompose hydrogen peroxide. In some respects, peroxide reducing agents are able to degrade at least about 500 ppm of hydrogen peroxide into a peracid composition in 15 minutes. In other respects, metals and / or potent oxidizing agents also have a high ability to decompose hydrogen peroxide in low concentrations. In some embodiments, the concentration of metals and / or potent oxidizing agents required to degrade 500 ppm of hydrogen peroxide in a peracid composition in 15 minutes is less than 200 ppm, less than 100 ppm, and less than 50 ppm.
[084] Beneficially, the reduction or elimination of hydrogen peroxide from oxidizing compositions alleviates the various inconveniences caused by the oxidizing agents of the various field operations for drilling wells, recovery and / or production applications (and others established in according to the methods of the invention). In particular, the use of peroxide reducing agents with the peracid compositions provides improved antimicrobial benefits without causing the damage associated with conventional oxidizing agents (for example, peracetic acid, hypochlorous acid or hypochlorite, and / or chlorine dioxide), such like corrosion. In an additional aspect, the reduction of hydrogen peroxide also benefits the stability of gel formation in gel fractionation fluids. Without being limited to a mechanism of the invention, the reduction of the hydrogen peroxide in a peracid composition beneficially allows a gel fractionation fluid to keep the gel for a sufficient period of time (before it dissipates within the underground environment) . In some respects, the reduction of hydrogen peroxide within a peracid composition according to the invention provides a suitable peroxide level from about 1 ppm to about 50 ppm, from about 1 ppm to about 25 ppm, or preferably from about 5 ppm to about 15 ppm to maintain a stable gel fractionation fluid over a long period of time.
[085] In one aspect, peroxide reducing agents preferably de-compose hydrogen peroxide from a peracid composition (for example, a higher percentage of peracid concentration remains in a treated peracid composition compared to the hydrogen peroxide). Without limiting the scope of peroxide reducing agents suitable for use according to the invention, in one aspect, the agent preferentially reduces hydrogen peroxide over peracid. In another aspect, the agent reduces at least about 2: 1 of hydrogen peroxide to peracid, or more. In another aspect, the agent reduces at least about 1.5: 1 of hydrogen peroxide to peracid, or more.
[086] In some embodiments, the peroxide reducing agent is able to degrade at least about 50% of the initial hydrogen peroxide concentration in a peracid composition. Preferably, the agent is supplied 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%, or at least about 90%. In some embodiments, the peroxide reducing agent reduces the hydrogen peroxide concentration of a peracid composition by more than about 90%. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[087] In one aspect of the invention, peroxide reducing agents are suitable for use and have a tolerance for a wide range of temperatures, including temperature ranges in water treatment applications, which can vary from about 0 ° C-180 ° C. Although temperature and other environmental conditions can affect the stability of the agents, an appropriate peroxide reducing agent will maintain at least 50% of its activity at storage and / or application temperatures of at least about 10 minutes, preferably for at least about 1 hour and more preferably for at least about 24 hours. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[088] In another aspect of the invention, the peroxide reducing agents described in this document have a tolerance for pH ranges found in water treatment applications. Levels of acetic acid (or other carboxylic acid) in a water treatment application can vary widely in parts per million (ppm) of acetic acid or another carboxylic acid. The solutions will have a corresponding pH range of more than 0 to about 10. An appropriate peroxide reducing agent will maintain at least about 50% of its activity in such acetic or other carboxylic acid solutions over a period of about 10 minutes, preferably for at least about 1 hour and more preferably for at least about 24 hours. Without limiting the scope of the invention, numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[089] In one aspect of the invention, a peroxide reducing agent is present in a solution for use in the treatment of water and peracid composition in amounts sufficient to reduce the concentration of hydrogen peroxide from the composition within peracid, at least a few hours, preferably within less than 10 hours, preferably within less than 5 hours, preferably within less than 4 hours, and even more preferably within less than 1 hour. In one aspect of the invention, a peroxide reducing agent is present in a solution for use in the treatment of water and the peracid composition in amounts sufficient to reduce the concentration of hydrogen peroxide from the peracid composition by at least 50 % at about 10 minutes, preferably within about 5 minutes, preferably within about 2 to 5 minutes, more preferably within about 1 minute. The concentration ranges of the agents can vary depending on the time period in which 50% of the hydrogen peroxide is removed from the peracid composition.
[090] In certain aspects of the invention, a peroxide reducing agent is present in a solution composition for use, including the source of water to be treated in amounts of at least about 0.5 ppm, preferably between about 0 , 5 ppm and about 1,000 ppm, preferably between about 0.5 ppm and about 500 ppm, preferably between about 0.5 ppm and 100 ppm, and most preferably between about 1 ppm and about 100 ppm. Without limiting the scope of the invention, numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[091] The peroxide reducing agents used can be free-floating in the composition of the use solution, which means that the agent is part of the composition, without being attached to a surface.
[092] Alternatively, the peroxide reducing agents can be immobilized on a surface that is in fluid communication with the composition of the use solution, in a way that allows the agent to interact and decompose hydrogen peroxide from peracid compositions. . In some respects, immobilized agents may be more stable than unbound, soluble agents. In some aspects, immobilized agents may also have greater thermal and pH stability, which may be due to the protection that substrate provides against sudden thermal and pH variations. An immobilized agent also has the advantage of being able to be easily removed from the rest of the composition. An immobilized agent can include an agent attached to a substrate. Examples of substrates may include, for example, zeolites, polyurethane foams, polyacrylamide gels, maleic anhydride polyethylene gels, maleic anhydride polystyrene gels, cellulose, nitrocellulose, silastic resins, porous glass, macro-porous glass membranes , glass microspheres, activated clay, zeolites, alumina, silica, silicate and other inorganic and organic substrates. The peroxide reducing agent can be attached to the substrate in several ways, including support covalent bonding, crosslinking, physical adsorption, ionic bonding and trapping.
[093] In one aspect, the peroxide reducing agent is added to a peracid solution instead of a concentrated peracid composition. Without being limited to a mechanism of action, the use of a peroxide reducing agent is preferably employed in a non-concentrated peracid composition in order to maintain the viability and capacity of the peroxide reducing agent. For example, in one aspect, a concentrated peracid composition (for example, about 10% by weight of peracid or more, or about 15% by weight of peracid or more) is diluted in a water source and subsequently the peroxide reducing agent is added. In one aspect, the diluted water source may be the source of water that needs treatment according to the invention. In another aspect, the water source can be diluted may be a solution for using the peracid composition (or the less concentrated peracid composition) for subsequent dosing at the water source, which requires treatment according to the invention. Peracids
[094] In some respects, a peracid is included for antimicrobial efficacy in water treatment compositions. As used herein, the term "peracid" can also be referred to as a "percarboxy acid" or "peroxyacid". Sulfoperoxycarboxylic acids, sulfonated peracids and sulfonated peroxycarboxylic acids are also included in the term "peracid" as used herein. The terms "sulfoperoxycarboxylic acid," "sulfonated peroxide" or "sulfonated peroxycarboxylic acid" refer to the peroxycarboxylic acid form of a sulfonated carboxylic acid as described in US Patent 8,344,026, and US Patent Publications numbers 2010/0048730 and 2012/0052134, each of which is incorporated into this document as a reference in its entirety. As one skilled in the art recognizes, a peracid refers to an acid with the hydrogen of the hydroxyl group in the carboxylic acid replaced by a hydroxy group. Oxidizing peracids may also be referred to herein as peroxycarboxylic acids.
[095] A peracid includes any compound of the formula R - (COOOH) n where R can be hydrogen, alkyl, alkenyl, alkaline, acyl group, alicyclic group, aryl, heteroaryl, or a heterocyclic group, and n is 1, 2 , or 3, and named for prefixing the present acid with peroxide. Preferably R includes hydrogen, alkyl, or alkenyl. The terms "alkyl", "alkenyl", "alkaline", "acyl", "alicyclic group", "aryl", "heteroaryl", and "heterocyclic group" are as defined herein.
[096] As used herein, 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, t-butyl (1,1-dimethylethyl) and the like. The term "alkyl" or "alkyl group" also refers to hydrocarbons saturated with one or more carbon atoms, including straight chain alkyl groups (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carboxylic groups") (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched chain alkyl groups (e.g., isopropyl, t-butyl-, sec-butyl, isobutyl, etc.), and alkyl groups substituted by alkyl (e.g. cycloalkyl groups substituted with alkyl and alkyl groups substituted by cycloalkyl).
[097] Unless otherwise specified, the term "alkyl" includes both "substituted alkyls" and "substituted alkyls. As used herein, the term" substituted alkyls "refers to alkyl groups with substitut- substituting one or more hydrogen atoms in one or more carbons of the hydrocarbon structure, such substituents may include, for example, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkyl , arylcarbonyl, alkoxycarbonyl, ami-nocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxy, phosphate, phosphonate, phosphinate, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino, arylaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoamilaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoaminoamino. , carbamoyl and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonate, sulfamoyl , sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or aromatic groups (including heteroaromatics).
[098] The term "alkenyl" includes an unsaturated aliphatic hydrocarbon chain having 2 to 12 carbon atoms, such as, for example, ethylene, 1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1 -propenyl and the like. The alkyl or alkynyl can be terminally substituted with a heteroatom, such as, for example, a nitrogen, sulfur, or an oxygen atom, forming an aminoalkyl, oxyalkyl, thioalkyl or, for example, aminomethyl, thioethyl, oxypropyl, and similar. Likewise, the above alkyl or alkenyl groups can be interrupted in the chain by a heteroatom forming an alkylaminoalkyl, alkylthioalkyl or alkoxyalkyl, for example, methylaminoethyl, ethylthiopropyl, methoxymethyl and the like.
[099] In addition, as used herein, the term "alicyclic" includes any cyclic hydrocarbon radical containing 3 to 8 carbon atoms. Examples of suitable alicyclic groups include cyclopropanyl, cyclobutanyl, cyclopentanyl, etc. The term "heterocyclic" includes any closed ring structure analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is a different element than carbon (heteroatom), for example, a nitrogen, sulfur, or an oxygen atom. Heterocyclic groups can be saturated or unsaturated. Examples of suitable heterocyclic groups include, for example, aziridine, ethylene oxide (epoxides, oxiranes), thyrane (episulfides), dioxirane, azetidine, oxethane, tiethane, dioxethane, dithietane, dithetide, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan. Additional examples of suitable heterocyclic groups include groups derived from tetrahydrofurans, furans, thiophenes, pyrrolidines, piperidines, pyridines, pyrrols, picoline, coumalin, etc.
[0100] According to the invention, alkyl, alkenyl, alicyclic groups, or heterocyclic groups can be substituted or unsubstituted by, for example, aryl, heteroaryl, C1-4 alkyl, C1-4 alkenyl, C1-4 alkoxy, amino , carboxy, halo, nitro, cyano, --SO3H2, phosphono or hydroxy. When the alkyl, alkenyl, alicyclic, or heterocyclic group is substituted, the substitution is preferably C1-4 alkyl, halo, nitro, starch, 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 aromatic heterocyclic derivatives with 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, wherein at least one ring is aromatic, such as, for example, indolyl, purinyl, benzofuryl, etc.
[0101] According to the invention, the aryl and heteroaryl groups can be substituted or unsubstituted on the ring by, for example, aryl, heteroaryl, alkyl, alkenyl, alkoxy, amino, carboxyl, halo, nitro, cyan, --SO3H , phosphono, or hydroxyl. When aryl, aralkyl or heteroaryl is substituted, preferably the substitution will be C1-4 alkyl, halo, nitro, starch, hydroxy, carboxy, sulfo or phosphono. In one embodiment, R includes C1-4 alkyl-substituted aryl.
[0102] Suitable peracids for use include any peroxycarboxylic acids, including various lengths of peroxycarboxylic and percarboxylic acids (eg, C1-22) that can be prepared from the catalyzed acid equilibration reaction between a carboxylic acid described above and hydrogen peroxide. A peroxycarboxylic acid can also be prepared by auto-oxidizing aldehydes or by reacting hydrogen peroxide with an acid chloride, acid hydride, carboxylic acid anhydride, or sodium alcoholate. Alternatively, peracids can be prepared through non-equilibrium reactions, which can be generated for use in situ, such as the methods described in US Patent Publications numbers 2012/0172440 and 2012/0172441 each entitled "In Situ Generation of Peroxicarboxylic Acids at Alkaline pH and Methods of Use Thereof "which are hereby incorporated by reference in their entirety. Preferably, a composition of the present invention includes peroxyacetic acid, peroxioctanoic acid, peroxypropionic acid, peroxylactic acid, peroxytanoic acid, peroxytanoic acid and / or peroxynonanoic acid.
[0103] In some embodiments, a peroxycarboxylic acid includes at least one water-soluble peroxycarboxylic acid, where R includes an alkyl group of 1-22 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 group of 1-22 carbon atoms, substituted with hydroxy. Methods of preparing peracetic acid are known to those skilled in the art, including those described in US Patent No. 2,833,813, which is hereby incorporated by reference in its entirety.
[0104] In another embodiment, a sulfoperoxycarboxylic acid has the following formula:

[0105] 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 a radical-forming ester; or its salts or esters. In some embodiments, R1 is a substituted or unsubstituted C1-6 alkyl group; X is hydrogen from a cationic group, or an ester-forming fraction, a radical-forming ester; R2 is a substituted or unsubstituted C8 alkyl group; m = 1 to 10; n = 1 to 10; and m + n is less than 18, or its salts, esters or mixtures.
[0106] In some modalities, R1 is hydrogen. In other embodiments, R1 is a substituted or unsubstituted alkyl group. In some embodiments, R1 is a substituted or unsubstituted alkyl group, which does not include a cyclic alkyl group. In some embodiments, R1 is a substituted alkyl group. In some embodiments, R1 is an unsubstituted C1-C9 alkyl group. In some embodiments, R1 is an unsubstituted C7 or C8 alkyl. In other embodiments, R1 is a substituted C8-C10 alkylene group. In some embodiments, R1 is a substituted C1-C9 alkyl group, it is substituted with at least one, or at least two hydroxyl groups. In still other embodiments, R1 is a substituted C1-C9 alkyl group. In some embodiments, R1 is a substituted C1-C9 alkyl group being replaced with at least one SO3H group. In other embodiments, R1 is a substituted C9-C10 alkyl group. In some embodiments, R1 is a substituted C9-C10 alkyl group where at least two carbon atoms in the carbon structure form a heterocyclic group. In some embodiments, the heterocyclic group is an epoxide group.
[0107] In some embodiments, R2 is a substituted C1-C10 alkylene group. In some embodiments, R2 is a C1-C10 alkylene group. In some embodiments, R2 is an unsubstituted C8-C10 alkylene. In other embodiments, R2 is a C8-C10 alkylene group substituted with at least one hydroxyl group. In some embodiments, R2 is a C10 alkylene group substituted with at least two hydroxyl groups. In other embodiments, R2 is a C8 alkylene group substituted with at least one SO3H group. In some embodiments, R2 is a substituted C9 group, in which at least two of the carbon atoms in the main carbon chain form a heterocyclic group. In some embodiments, the heterocyclic group is an epoxide group. In some embodiments, R1 is substituted or unsubstituted C8-C9 alkyl and R2 is a substituted or unsubstituted C7-C8 alkylene group.
[0108] These and other sulfoperoxycarboxylic acid compounds suitable for use in the stabilized peroxycarboxylic acid compositions of the invention are further disclosed in US Patent No. 8,344,026 and US Patent Publications 2010/0048730 and 2012/0052134, which are incorporated herein. as a reference in its entirety.
[0109] In the additional embodiments, a sulfoperoxycarboxylic acid is combined with a simple or mixed peroxycarboxylic acid composition, such as a sulfoperoxycarboxylic acid with peracetic acid, peroxioctanoic acid and sulfuric acid (PSOA / POOA / POAA / H2SO4). In other embodiments, a mixture of peracids is employed, such as a peroxycarboxylic acid, including at least one peroxycarboxylic acid of limited solubility in water, where R includes an alkyl group of 5-22 carbon atoms and at least one acid peroxycarboxylic, soluble in water, where R includes alkyl of 1-4 carbon atoms. For example, in one embodiment, a peroxycarboxylic acid includes peroxyacetic acid and at least one other peroxycarboxylic acid such as those mentioned above. Preferably, a composition of the present invention includes peracetic acid and peroxioctanoic acid. Other combinations of mixed peracids are well suited for use in the present invention.
[0110] In another embodiment, a mixture of peracetic acid and peroctanoic acid is used to treat a source of water, as disclosed in US Patent number 5,314,687 which is incorporated into this document as a reference in its entirety. 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 peracid mixing system allows the use of lower doses of peracids.
[0111] In another embodiment, a tertiary peracid mixture composition, such as peroxysulfonated oleic acid, peracetic acid and peroctanoic acid is used to treat a source of water, as disclosed in US Patent number 8,344,026 which is incorporated into the this document as a reference in its entirety. A combination of the three peracids provides significant antimicrobial synergy providing an effective antimicrobial composition for the water treatment methods according to the invention. In addition, the high acidity built into the composition is thought to aid in the removal of chemical contaminants from water (for example, sulphite and sulphide species), and the antifoaming agent (for example, aluminum sulphate) provides foaming (for example, example, combating foam caused by any anionic surfactants used in water treatment).
[0112] Advantageously, a combination of peroxycarboxylic acids provides a composition with desirable antimicrobial activity in the presence of high organic soil loads. Mixed peroxycarboxylic acid compositions often provide synergistic antimicrobial efficacy. Thus, the compositions of the invention can include a peroxycarboxylic acid or mixtures thereof.
[0113] Several commercial formulations of peracids are available, including, for example, peracetic acid (15%) and hydrogen peroxide (10%) available as EnviroSan (Ecolab, Inc., St. Paul MN). Most commercial peracid solutions indicate a specific concentration of percarboxylic acid, without reference to other chemical components in a solution in use. However, it should be understood that commercial products, such as peracetic acid, also contain the corresponding carboxylic acid (for example, acetic acid), hydrogen peroxide and water.
[0114] In one aspect, any 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, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18 , C19, C20, C21, or C22. In still other embodiments, the C1-C22 percarboxylic acid comprises peroxyacetic acid, peroxioctanoic acid and / or peroxysulfonated oleic acid.
[0115] In one aspect of the invention, a peracid is present in the use of a solution with the water source, which requires treatment in an amount between about 1 ppm and about 5,000 ppm, preferably between about 1 ppm and about 2,000 ppm, preferably between about 1 ppm and about 1,000 ppm, and most preferably between about 1 ppm and about 100 ppm. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and each include an integer within the defined range. The amount of peracid above the preferred range of 100 ppm can be used for highly contaminated waters that need treatment, such as spring waters, including increasing the amount of water derived from production (for example, recycled water).
[0116] In one aspect of the invention, a peracid can be selected from a concentrated composition having a hydrogen peroxide to peracid ratio between about 0: 100 to about 0.5: 100, preferably about 0 , 5: 100 and about 1:10. Various concentrated peracid compositions containing hydrogen peroxide to peracid ratios of about 0: 100 to about 0.5: 100, preferably about 0.5: 100 and about 1:10 can be used to produce a use solution for the treatment according to the methods of the invention. In another aspect of the invention, a peracid may have a hydrogen peroxide to peracid ratio as low as about 0.001 part or 0.01 part hydrogen peroxide to about 1 part peracid. Preferably, any proportion in which the amount of hydrogen peroxide is less than the peptide is suitable for use according to the invention in the formulation of a solution for the use of water treatments. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[0117] The preferred hydrogen peroxide to peroxycarboxylic acid ratios in a peracid composition can be obtained by a variety of methods suitable for producing a very low hydrogen peroxide to peroxide ratio. In one aspect, equilibrium peracid compositions can be distilled to recover a very low mixture of peracid and hydrogen peroxide. In yet another aspect, catalysts for hydrogen peroxide decomposition can be combined with a peracid composition, including, for example, peroxide reducing agents and / or other biomimetic complexes. In yet another aspect, the perhydrolysis of peracid precursors, such as esters (eg, triacetin) and amides can be used to obtain peracids with a very low hydrogen peroxide content.
[0118] In a particularly preferred aspect, the ester precursors and amide peracid show alkyl leaving groups varying in the lengths of the C1-C8 carbon chain. In each of these aspects, the concentration of peroxycarboxylic acid ranges from 0.0001% by weight to 20% by weight, preferably from about 0.0001% by weight to 10% by weight, or from about 0.0001% by weight up to 5% by weight, or from about 1% by weight to about 3% by weight. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[0119] In one aspect of the invention, a peroxide reducing agent is combined with a peracid composition. In one aspect, a peracid composition with a concentration of less than or equal to about 10% can be combined with the peroxide reducing agent, without having a negative effect on the peroxide reducing agent. In another preferred aspect, a peracid composition with a concentration less than or equal to about 5% is suitable for use with the peroxide reducing agent, without having a negative effect on the peroxide reducing agent. In an even more preferred aspect, a peracid concentration less than or equal to 3% is preferred, or less than or equal to 2%. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range. Hydrogen peroxide
[0120] The present invention includes reduced amounts of hydrogen peroxide, and preferably no hydrogen peroxide. Hydrogen peroxide, H2O2, provides the advantages of having a high proportion of active oxygen due to its low molecular weight (34.014 g / mol) and being compatible with numerous substances that can be treated by the methods of the invention, since it is a clear, colorless and slightly acidic liquid. Another advantage of hydrogen peroxide is that it decomposes into water and oxygen. It is advantageous to have such decomposition products, because they are generally compatible with the substances to be treated. For example, decomposition products are generally compatible with metallic substances (for example, substantially non-corrosive) and are generally harmless to accidental contact and are environmentally friendly.
[0121] In one aspect of the invention, hydrogen peroxide is present, initially, in an antimicrobial peracid composition in an amount effective to maintain the balance between a carboxylic acid, hydrogen peroxide, water and a peracid. The amount of hydrogen peroxide must not exceed an amount that adversely affects 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 in a concentration as close to zero as possible. That is, the concentration of hydrogen peroxide is minimized through the use of reducing agents selected from peroxide according to the invention. In other respects, the concentration of hydrogen peroxide is reduced and / or eliminated, as a result of the distilled equilibrium peracid compositions, other catalysts for the decomposition of hydrogen peroxide (for example, biomimetic complexes) and / or the use of ester perhydrolysis (eg, triacetin) to obtain peracids with very low hydrogen peroxide content.
[0122] According to the invention, an advantage of minimizing the concentration of hydrogen peroxide is that the antimicrobial activity of a composition of the present invention is improved compared to conventional equilibrium peroxide compositions. Without being limited to a specific theory of the invention, the significant improvements in antimicrobial efficacy result from improved peracid, namely the POAA stability from the reduced concentration of hydrogen peroxide.
[0123] In one aspect of the invention, hydrogen peroxide may typically be present in an in-use solution in an amount of less than 2,500 ppm, preferably less than 2,000 ppm, more preferably less than 1,000 ppm. In preferred embodiments, the use of a catalase reduces the concentration of hydrogen peroxide as close to zero as possible, preferably a concentration of zero. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range. In other aspects of the invention, hydrogen peroxide in a peracid composition is reduced by at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%. Preferably, the hydrogen peroxide is substantially zero after treatment of a peracid composition according to the invention. In the additional aspects, the ratio of hydrogen peroxide to peracid in a concentrated composition for use according to the invention is from about 0: 100 to about 1:10, preferably from about 0.5: 100 and about 0.5: 10. Various concentrated peracid compositions with a hydrogen peroxide to peracid ratio of about 0: 100 to about 1:10, preferably about 0.5: 100 and about 0.5: 10, can be used to to produce a solution of use for the treatment according to the invention. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[0124] In another aspect, a usage solution can have a hydrogen peroxide to peracid ratio as low as about 0.001 part of hydrogen peroxide to about 1 part of peracid. Preferably, any reason in which the amount of hydrogen peroxide is less than peracid will be suitable for use according to the invention in formulating a solution for use in water treatment. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range. Carboxylic Acid
[0125] 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, alkaline, acyl, alicyclic group, aryl, heteroaryl, or a heterocyclic group, and n is 1, 2, or 3 Preferably R includes hydrogen, alkyl, or alkenyl. The terms "alkyl", "alkenyl", "alkaline", "acyl," "alicyclic group", "aryl", "heteroaryl" and "heterocyclic group" are as defined above with respect to peracids.
[0126] Examples of suitable carboxylic acids according to the peracid balance systems according to the invention include a variety of monocarboxylic acids, dicarboxylic and tricarboxylic acids. Monocarbonyl acids include, for example, formic acid, acetic acid, propanoic, butanoic, pentanoic, hexanoic acid, heptanoic acid, octanoic acid, nonaic 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, galcic acid, etc.
[0127] In one aspect of the invention, a particularly well-adapted 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 present invention includes acetic acid, octanoic acid or propionic acid, lactic acid, heptanoic acid, octanoic acid or nonanoic acid. Other examples of suitable carboxylic acids used in sulfoperoxycarboxylic acid or sulfonated peracid systems are disclosed in US Patent number 8,344,026, and in US Patent Publication 2010/0048730 and 2012/0052134, each of which is incorporated herein as reference in its entirety.
[0128] Any C1-C22 carboxylic acid can be used in the present compositions. In some embodiments, C1-C22 percarboxylic acid is a C2-C20 percarboxylic acid. In other embodiments, the C1-C22 carboxylic acid is a C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, carboxylic acid, C19, C20, C21, or C22. In still other embodiments, C1-C22 carboxylic acid comprises acetic acid, octanoic acid and / or sulfonated oleic acid.
[0129] In one aspect of the invention, a carboxylic acid is present in a solution for use with the water source, which requires treatment in an amount between about 1 ppm and about 5,000 ppm, preferably between about 1 ppm and about 2,000 ppm, preferably between about 1 ppm and about 1,000 ppm, and most preferably between about 1 ppm and about 100 ppm. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range. The amount of carboxylic acid above the preferred range of 100 ppm can be used for highly contaminated water that needs treatment, such as spring water, including increasing the amount of water derived from production (eg, recycled water). Additional optional materials
[0130] The composition may optionally include additional ingredients to improve 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 descaling agents (ie scale inhibitors), surfactants and / or additional antimicrobial agents for increased effectiveness (for example, mixed peracids, biocides, antifoaming agents), UV blocking agents, acidulants (for example, strong mineral acids) or other pH modifiers, additional carboxylic acids, and the like. In one embodiment, no additional functional ingredients are employed. Friction Reducers
[0131] 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 desired permeability of the gas and / or oil being recovered from the cracks or pathways conductors of fluid created through the fractionation process. Friction reducers allow water to be pumped into formations more quickly. Various polymeric additives have been widely used as friction reducers to improve or modify the characteristics of aqueous fluids used in drilling wells, and recovery and production applications.
[0132] Examples of commonly used friction reducers include polyacrylamide polymers and copolymers. In one aspect, suitable additional friction reducers may include polymers derived from acrylamide and copolymers, such as, polyacrylamide (sometimes abbreviated as PAM), acrylamide-acrylate (acrylic acid co-polymers), acrylic acid-methacrylamide copolymers, partially hydrolyzed polyacrylamide (PHPA) copolymers, partially hydrolyzed polymethacrylamide, acrylamide-methyl-propane sulfonate (AMPS) copolymers and the like. Various derivatives of such polymers and copolymers, for example, quaternary amine salts, hydrolyzate versions, and the like are to be understood as being included with the polymers and copolymers described herein.
[0133] Friction reducers are combined with water and / or other aqueous fluids, which in combination are often referred to as "fracturing water fluids". Fracturing water fluids have reduced frictional drag and beneficial flow characteristics that allow the pumping of aqueous fluids in various gas and / or oil producing areas, including, for example, fracturing.
[0134] In one aspect of the invention, a friction reducer is present in the use of a solution in an amount between about 100 ppm to 1,000 ppm. In another aspect, a friction reducer 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, 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. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[0135] Beneficially, the compositions and methods of the invention do not interfere negatively with friction reducers included in an aqueous solution. Without being limited to a specific theory of the invention, it is believed that the reduction and / or elimination of the hydrogen peroxide oxidant from the peracid composition promotes the stability and effectiveness of any variation in the amount of the friction reducer present in a solution of use. Viscosity boosters
[0136] Viscosity enhancers are additional polymers used in water or other water-based fluids used in hydraulic fracturing treatments to improve viscosity. Polymers that increase natural and / or synthetic viscosity can be used in compositions and methods according to the invention. Viscosity enhancers can also be referred to as gelling agents and examples include guar, xanthan, cellulose derivatives and polyacrylamide and polyacrylate polymers in addition to copolymers and the like.
[0137] In one aspect of the invention, a viscosity enhancer is present when using a solution in an amount between about 100 ppm to 1,000 ppm. In another aspect, a viscosity enhancer is present when using a 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. 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, from 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. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[0138] Beneficially, the compositions and methods of the invention do not interfere negatively with viscosity enhancer included in an aqueous solution. Without being limited to a specific theory of the invention, it is believed that the reduction and / or elimination of the hydrogen peroxide oxidizer from the peracid composition promotes the stability and effectiveness of any variation in the amount of viscosity enhancer present in the solution a use. Corrosion Inhibitors
[0139] Corrosion inhibitors are additional molecules used in oil and gas recovery operations. Corrosion inhibitors that can be used in the present description are disclosed in US Patent number 5,965,785, US Patent Publication No. 2010/0108566, GB Patent number 1,198,734, WO / 03/006581, WO04 / 044266, WO08 / 005058 and, each of which is incorporated into these documents as a reference in its entirety.
[0140] In one aspect of the invention, a corrosion inhibitor is present in a solution for use in an amount between about 100 ppm to 1,000 ppm. In a further aspect, a corrosion inhibitor is present in a solution for use in an amount of at least about 0.0001% by weight to about 10% by weight, preferably at least about 0.0001% by weight. 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 0.0001% by weight to about 0.05% by weight. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[0141] Beneficially, the compositions and methods of the invention do not interfere negatively with the corrosion inhibitor included in an aqueous solution. Without being limited to a specific theory of the invention, it is believed that the reduction and / or elimination of the hydrogen peroxide oxidizer from the peracid composition promotes the stability and effectiveness of any variation in the amount of corrosion inhibitor present in a solution of use. Scale inhibitors
[0142] 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.
[0143] In one aspect of the invention, a scale inhibitor is present in the use solution in an amount between about 100 ppm to 1,000 ppm. In an additional aspect, a scale inhibitor is present in the solution for use in an amount of at least about 0.0001% by weight to about 10% by weight of at least about 0.0001% by weight. 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 Weight. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range.
[0144] Beneficially, the compositions and methods of the invention do not interfere negatively with scale inhibitor included in an aqueous solution. Without being limited to a specific theory of the invention, it is believed that the reduction and / or elimination of oxidizing hydrogen peroxide of the peptide composition promotes the stability and efficacy of any variation in the amount of the scale inhibitor present in a use solution. Additional antimicrobial agents
[0145] Additional antimicrobial agents can be included in the compositions and / or methods of the invention, for greater antimicrobial effectiveness. In addition to the use of peracid mixture compositions, additional antimicrobial agents (e.g., bioactive) and biocides can be employed. Additional biocides may include, for example, a quaternary ammonium compound as disclosed in US Patent No. 6,627,657, which is incorporated herein by reference in its entirety. Advantageously, the presence of the quaternary ammonium compound provides both synergistic antimicrobial efficacies with peracids, as well as sustaining the long-term biocidal efficacy of the compositions.
[0146] In another embodiment, the additional biocide may include an oxidant-compatible phosphonium biocide, such as tributyl-tetradecyl phosphonium chloride. Phosphonium biocide provides antimicrobial advantages similar to the quaternary ammonium compound in combination with peracids. In addition, the phosphonium biocide is compatible with the anionic polymer chemicals commonly used in applications in oil fields, such as the fractionation methods disclosed according to the invention.
[0147] Additional antimicrobial agents and biocides can be used in sufficient quantities to provide antimicrobial efficacy, as they may vary depending on the source of the water that needs treatment and the contaminants in it. These agents can 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, more preferably from about 0.1% by weight to about 10% by weight. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range. Acidulants
[0148] Acidulants can be included as additional functional ingredients in the composition according to the invention. In one aspect, a potent, oxidative mineral acid, such as nitric acid or sulfuric acid, can be used to treat source water, as disclosed in US Patent No. 4,587,264, which is incorporated herein by reference in its wholeness. For example, the combined use of a potent mineral acid with the peracid composition provides greater antimicrobial efficacy, as a result of the auxiliary acidity in removing chemical contaminants within the water source (for example, sulphite and sulphide species). In one aspect of the invention, the use of an acidulant, such as a mineral acid, is suitable for lowering the pH of the water source and / or the treated peracid composition to obtain an additional and / or synergistic impact on cleaning efficacy .
[0149] In one aspect, an acidulant can be used to lower the pH of the water source, which needs treatment at a pH below about 6, preferably below about 5, and more preferably between about 4.5 and about 5.5 to achieve a synergistic effect in cleaning water from acid. In a preferred aspect, an acidulant is used to lower the pH of the treated water source from about 2 to about 6 to provide a synergistic impact on the cleaning water. According to this modality, any acidifying agent can be used to lower the pH of the water source. Examples of suitable acidulants include hydrochloric acid and other acids, and chlorine, chlorine dioxide (ClO2) and other oxidizing agents.
[0150] In addition, some potent mineral acids, such as nitric acid, provide an additional benefit of reducing the risk of corrosion to metals contacted by the peracid compositions according to the invention. Examples of peracid products containing nitric acid are commercially available from Envirotech Chemical Services, Inc. (Reflex brand) and Solvay Chemicals (Proxitane®).
[0151] In an additional aspect, an acidulant can be employed to reduce the pH of the peracid composition according to the invention to increase the stability of the peracid, decreasing the pH of the peracid composition. For example, in some embodiments, lowering the pH of the treated peracid composition from about 8 or more to less than about 8 or less than about 7.5, or less than about 7 has a beneficial impact on stability of the peracid for use according to the methods of the invention.
[0152] Acidulants can be used in sufficient quantities to provide the desired antimicrobial effect, stability of the peracid and / or anti-corrosion benefits, as they may vary depending on the composition of peracid and / or water source requiring treatment and the contaminants in them. These agents can 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 at about 20% by weight, more preferably from about 0.1% by weight to about 10% by weight. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range. Peracid Stabilizers
[0153] In some embodiments, the compositions of the present invention include one or more stabilizing agents. Stabilizing agents can be used, for example, to stabilize hydrogen peroxide and peracid and prevent premature oxidation of that constituent within the composition of the invention.
[0154] In some embodiments, an acidic stabilizing agent can be used. Thus, in some embodiments, the compositions of the present invention can be substantially free of an additional acidulant.
[0155] Suitable stabilizing agents include, for example, chelating or sequestering agents. Suitable sequestrants include, but are not limited to, organic chelating compounds that sequester metal ions in solution, particularly transition metal ions. Such sequestrants include complexing agents of organic amino or hydroxy-polyphosphonic (either in the form of acid or soluble salt), carboxylic acids (for example, polymeric polycarboxylate), hydroxycarboxylic acids, aminocarboxylic acids, carboxylic or heterocyclic acids, for example example, pyridine-2,6-dicarboxylic (dipicolinic acid).
[0156] In some embodiments, the compositions of the present invention include dipicolinic acid as a stabilizing agent. Compositions that include dipicolinic acid can be formulated to be free or substantially free of phosphorus.
[0157] In other embodiments, the scavenger may be or include phosphonic acid or phosphonate salt. Phosphonic acids and suitable phosphonate salts include HEDP; ethylenediamine tetracis methylenephosphonic acid (EDTMP); diethylene triamine pentacis methylene acid (DTPMF); cyclohexane-1,2-tetramethylene phosphonic; amino [tri (methylene phosphonic acid)]; (ethylenediamine [methylene-phosphonic acid tetra)]; 2-phosphene butane-1,2,4-tricarboxylic acid; or its salts, such as the alkali metal salts, ammonium salts or alkyl alkyl amine salts, such as mono, di, or tetra-ethanolamine salts; dipicolinic acid, picolinic or mixtures thereof. In some embodiments, organic phosphonates, for example, HEDP are included in the compositions of the present invention.
[0158] Chelating agents, commercially available food additives include phosphonates sold under the trade name Dequest®, including, for example, 1-hydroxyethylidene-1,1-diphosphonic acid, available from Monsanto Industrial Chemicals Co., St. Louis, MO , such as Dequest® 2010; amino (tri (methylenephosphonic acid)), (N [CH2PO3H2] 3), available from Monsanto as Dequest® 2000; ethylenediamine [tetra (methylenephosphonic acid)] available from Monsanto as Dequest® 2041; and 2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay Chemical Corporation, Inorganic Chemicals Division, Pittsburgh, PA, as Bayhibit AM.
[0159] The sequestering agent can be or include aminocarboxylic acid type sequestrant. Suitable aminocarboxylic acid type sequestrants include alkali metal acids or salts, for example, amino acetates and their salts. Suitable aminocarboxylates include diacetic N-hydroxyethylamino acid; hydroxyethylenediaminetetraacetic acid, nitrilatriacetic acid (NTA); ethylenediamine tetraacetic acid (EDTA); N-hydroxyethyl ethylenediamine triacetic acid (HEDTA); diethylenetetraminopenta acetic acid (DTPA); and alanine-N, N-diacetic acid; and similarly to mixtures thereof.
[0160] The sequestering agent can be or include a polycarboxylate. Suitable polycarboxylates include, for example, polyacrylic acid, maleic acid / olefin copolymer, acrylic / maleic copolymer, polymethacrylic acid, methacrylic acid-acrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polyolamide, hydrolyzed polyolamides, polyolamides, hydrolysed polyolamides, hydrolyzed polyolamides , hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, polymalleic acid, polyfumaric acid, copolymers of acrylic acid and itaconic acid, polycarboxylate phosphate, forms of the same, and mixtures thereof.
[0161] In certain embodiments, the present composition comprises about 0.01 to about 10% by weight of stabilizing agent, about 0.4 to about 4% by weight of stabilizing agent, about 0.6 to about from 3% by weight of stabilizing agent, from about 1 to about 2% by weight of stabilizing agent. It is to be understood that all values and ranges between these values and ranges are encompassed by the present invention. UV blocking agent
[0162] The compositions according to the invention can also include a UV blocking agent and / or absorbent agent. In one aspect, a UV blocking agent is any agent that prevents and / or reduces the amount of exposure to ultraviolet (UV) radiation from a water source in need of treatment according to the invention. As established according to the methods of the invention, in the alternative of a UV blocking agent, the methods of use can be employed to minimize and / or eliminate exposure to sunlight by dosing the peroxide reducing agent at a time, with no or low exposure to UV radiation, such as during the night and / or periods of cloudy weather. However, one skilled in the art will understand that the reference to UV reduction and / or blocking according to the invention will include one or both of these scenarios.
[0163] In one aspect, the UV blocking agent can include natural dyes (from a variety of sources) and / or synthetics that are compatible with the peracid compositions employed in accordance with the compositions and methods of the present invention. As noted herein, synthetic dyes include organic dyes, including, for example, acid dyes and / or basic dyes. Preferably, the dyes are soluble in water. In one aspect, UV blocking agents may include a dye, a means of covering a water source, or the like, which are suitable for reducing and / or preventing sunlight from entering a water system that requires treatment. In one respect, dyes suitable for use as UV blocking agents are those that are capable of preventing and / or reducing the penetration of sunlight into a water system.
[0164] In one aspect, the dye is a blue dye showing considerable absorption in the ultraviolet regions. In an exemplary embodiment, the dye is, for example, methylene blue (for example, methyltioninium chloride). In other respects, the dye is a cationic dye. In other respects, the dye is a heterocyclic aromatic compound.
[0165] In a preferred aspect, the dye used as a UV blocking agent still has antimicrobial properties, such as the methylene blue dye blue. In an even more preferred aspect, the dye used as a UV blocking agent still has anti-algae properties. Without being limited to a particular mechanism of action and / or the theory of the invention, the UV blocking agent, in addition to preventing and / or reducing the penetration of sunlight into a water system, provides even more the antimicrobial properties and / or anti-algae that provides additional benefit (s) for the condition of the water source, in addition to the advantage of allowing the peroxide reducing agent (eg catalase) to work to reduce the hydrogen peroxide content in a usage solution . Such additional benefits provided to the water source through the use of UV blocking and anti-algae and / or antimicrobial agents can prolong the frequency of dosing the treated peracid composition.
[0166] In one aspect, the UV blocking agent can be supplied and / or formulated in a composition with the peroxide reducing agent according to the invention. In an alternative aspect, the UV blocking agent can be supplied separately from both the peracid composition and / or the peroxide reducing agent. According to such embodiments of the invention, the UV blocking agent can be formulated in a two- or three-part system for the treatment of a water source according to the methods of the invention.
[0167] In one aspect of the invention, a UV blocking agent is supplied in use solution in an amount of about 0.1 ppm to about 5,000 ppm, preferably between about 1 ppm to about 2,000 ppm, more preferably from about 1 ppm to about 500 ppm. Without limiting the scope of the invention, the numerical ranges are inclusive of the numbers that define the range and individually include an integer within the defined range. Methods of Use
[0168] In some aspects, the processes presented for water treatment in the recovery of gas and oil provide effective antimicrobial efficacy, without any harmful interaction with functional agents, including friction reducers, for example. In a further aspect, the methods for treating water according to the invention, using the peroxide reducing agent, provide greater antimicrobial efficacy compared to the use of antimicrobial peracids alone. In an additional aspect, the methods of use result in the elimination of cleaner water with low numbers of microorganisms. In a further aspect of the processes of the invention, the reduction and / or elimination of H2O2 from the peracid compositions minimizes the negative effects of the H2O2 oxidant. Use in Water Treatment
[0169] Treated peracid compositions (ie, peracid compositions with little or no hydrogen peroxide) can be used for a variety of industrial applications, for example, to reduce microbial or viral populations on a surface or object, or in an organ or flow of water. In some respects, the invention includes methods of using 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 fouling in liquid systems, water derived from processes or on the surfaces of equipment that come into contact with such liquid systems. As stated in this document, microbial contamination can occur in various industrial liquid systems, including, but not limited to, aerial contamination, waste water, process leaks and inadequately cleaned equipment. In another aspect, the peracid compositions and peroxide reducing enzyme agent (eg, catalase peroxide) (or other treated peracid compositions having a low content of substantially no hydrogen peroxide) are used to control the growth of microorganisms. in the water used in various oil and gas operations. In another aspect, the compositions are suitable for incorporation into fracturing fluids to control or eliminate microorganisms.
[0170] As used herein for the methods of the invention, peracid-treated compositions can employ a variety of peracid compositions with a substantially low or none hydrogen peroxide concentration. These peracid treated compositions include peracid compositions with a peroxide reducing agent to reduce hydrogen peroxide to the peracid ratio and / or other peracid compositions with reduced hydrogen peroxide content disclosed in the compositions herein. In a preferred embodiment, solutions using peracid and peroxide reducing agent with low or none hydrogen peroxide content are introduced to a water source that needs treatment
[0171] The methods by which the solutions for the use of treated peracids are introduced into the aqueous fluids according to the invention are not critical. The introduction of treated peracid compositions (and / or the introduction of two or more parts of the system, such as a peracid composition and a peroxide reducing agent composition, can be carried out continuously or intermittently, and will depend on the type of water to be treated.
[0172] In one aspect, the solutions of use of treated peracids are employed according to the methods of the invention. As noted herein, treated peracid compositions or treated peracid use solutions are understood to refer to peracid compositions having low or no hydrogen peroxide content. Such low content peracid compositions or substantially no hydrogen peroxide can be generated through the use of a peroxide reducing agent (s) at a point of use (for example, the combination of more than one component of the composition - for example, the peroxide reducing agent and a peracid composition in a two-part system) and / or generated before a point of use.
[0173] In one aspect, treated peracid compositions are generated at a point of use, and can be generated within a water source on site. In one aspect, the peracid composition and a peroxide reducing agent, such as a metal and / or strong oxidizing agent, are combined with a water source at a point of use and the hydrogen peroxide concentration of the solution to be used. it is reduced over a period of time of at least one minute to a few hours, preferably from at least 5 minutes to a few hours. One skilled in the art will find that the treatment time for a solution using a peracid composition within a source of water to be treated will vary, depending on the concentration of the peroxide reducing agent and / or the volume of the peracid composition and / or water source that needs treatment. The concentrations of the composition of peracid and peroxide reducing agent will also vary depending on the amount of bacteria inside the water source, which needs treatment.
[0174] In one aspect, treated peracid solutions may further comprise a UV blocking agent and / or other means to minimize and / or prevent exposure to UV rays from treated peracid solutions and / or water , which requires treatment with the peracid compositions. Without being limited to a theory or mechanism of the invention, in particular, the use of UV blocking agents (or other means to minimize and / or prevent exposure to UV rays) allows the effective reduction of the concentration of hydrogen peroxide within a peracid composition according to the invention.
[0175] In one aspect, a suitable UV blocking agent is provided in a peracid composition. Beneficially, the use of UV blocking agents described is stable for the formulation within the peptide compositions. In another aspect, the UV blocking agent can be added directly to a water source in need of treatment, either simultaneously with the peracid composition or in sequence with the peracid compositions.
[0176] In still other aspects, the UV blocking agent can alternatively be replaced with the application methods of the compositions of peracids that effectively minimize exposure to sunlight (for example, the dosage of the reducing agent of sunlight). peroxide at a time, without and / or in poor sunlight, such as during the night and / or foggy periods of time). In still other aspects, the UV blocking agent can refer to a coating that physically blocks sunlight from the water source.
[0177] In one aspect, the solutions for using treated peracids are added to the waters that need treatment before the drilling and fractionation steps, in order to limit the introduction of microbes into the reservoir and to prevent microbes from having a negative effect on fluid integrity. The treatment of source water (for example, pond, holding tank, lake, municipal, etc.) and / or water derived from production is particularly well suited to the use according to the invention.
[0178] The waters treated according to the invention can be used both for the fracturing of the fracturing water (that is, using friction reducers) and / or fracturing in gel (that is, using viscosity enhancers), depending on the type formation to be fractured and the type of hydrocarbon that must be produced. Use of a treated peracid solution, that is, a peracid composition solution treated with peroxide reducing agent having a low to substantially none of hydrogen peroxide content, is suitable for both fracturing with fracturing water and fracturing with gel.
[0179] In one aspect, pretreating the peracid composition, such as peracetic acid (including a mixture of acetic acid, hydrogen peroxide and water) with a peroxide reducing agent substantially eliminates hydrogen peroxide with a minimum or no impact on the fractionation fluids and the well itself. In one aspect, peracetic acid treated with a peroxide reducing agent allows the formation of a suitable gel for gel fracture, unlike untreated hydrogen peroxide / peracetic acid solutions that do not allow a gel to form. In another aspect, the solutions for the use of treated peracids are added to the waters that need treatment in underground well formations (for example, introduced through a hole in an underground formation). These methods provide an additional control in the formation well suited for the reduction of the microbial populations already present inside the well pipe or inside the reservoir itself.
[0180] In an additional aspect, treated peracid solutions are added to waters that need treatment before disposal. In this respect, the recirculation water (eg, post-fractionation) is treated to minimize microbial contamination in the water and to remove solids before disposal of water in an underground well, reuse in a subsequent fracturing application or return of water for local environmental water sources.
[0181] In an alternative aspect, the solution of using peracid can be formed inside the source of water to be treated. For example, a peracid composition is provided to a water source and a peroxide reducing agent is then supplied to the water source, such that the reduction and / or elimination of the peroxide concentration occurs within the water source. These methods provide an additional control in the formation well suited for the reduction of the microbial populations already present inside the tubing in the well or inside the reservoir itself.
[0182] In one aspect of the invention, methods of treating a water source may include cyclical dosing of treated peracid compositions (e.g., low or no hydrogen peroxide) to a water source. In an alternative aspect, methods of treating a water source may include the cyclic dosage of a water source with a composition of two (or more) parts used to generate the treated peracid composition (for example, low or no content) hydrogen peroxide) inside the water source that needs treatment. Such cyclic dosage may include the daily dosage, the dosage every two or more days, all dosages of three or more days, all dosages four or more days, all dosages of five or more days, all dosages of six or more more days, the weekly dose or more frequent dosage. In a preferred aspect, the water source is treated in a cycle every five days for the reduction or optimal elimination of hydrogen peroxide within a peptide composition used to treat the water source. Without being limited according to the mechanism and / or scope of the invention, all intervals of administration cycles are included within the scope of the invention. In one aspect, the present invention is directed to a method for the treatment of water, which method comprises providing the above compositions to a water source that needs treatment to form a treated water source, wherein said water source Treated water comprises about 1 ppm to about 1,000 ppm of said C1-C22 percarboxylic acid. Any C1-C22 percarboxylic acid can be used in the present methods. For example, peroxyacetic acid, peroxioctanoic acid and / u peroxysulfated oleic acid can be used. In some embodiments, a combination of peroxyacetic acid, peroxioctanoic acid and peroxysulfonated oleic acid is employed.
[0183] The treated peracid composition provides a source of water with any suitable concentration of hydrogen peroxide. In some embodiments, the source of treated water comprises from about 1 ppm to about 15 ppm of hydrogen peroxide. In other embodiments, the source of treated water comprises about 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 11 ppm, 12 ppm, 13 ppm , 14 ppm, or 15 ppm of hydrogen peroxide.
[0184] In one aspect, treated peracid solutions can be added to a water inlet stream, such as water added to a holding tank or other storage reservoir. In one embodiment, the solutions for using treated peracids are added to provide a concentration of peracid (eg, peracetic acid) applied at a rate of about 1 ppm to about 5,000 ppm peracid, from about 1 ppm at about 2,000 ppm, from about 1 ppm to about 1,000 ppm, from about 1 ppm to about 500 ppm, and preferably from about 1 ppm to about 100 ppm of peptide. Without being limited according to the mechanism and / or scope of the invention, all ranges are included within the scope of the invention.
[0185] In an alternative aspect, treated peracid solutions can be added at a high concentration of peracid (for example, about 200 to about 5,000 ppm) to an intermittent water source (for example, a water tank) shorter hold, such as up to about 37.84 hectoliters of water) before dilution in a larger hold tank or other storage reservoir for a water source (for example, 37,854 hectoliters of water or more). Upon such dilution inside a water source the peracid is rapidly diluted to a preferred rate of about 0.1 ppm to about 100 ppm peracid, preferably from about 1 ppm to about 100 ppm peracid. Without being limited to a mechanism of action, such a method beneficially provides a quick extermination of microorganisms within a smaller / controlled volume of a water source that needs treatment, while continuing to provide a static or slower antimicrobial activity. inside a volume water system.
[0186] In yet another alternative aspect, the solutions for using treated peracids can be added to a fluid of larger, larger quantities, such as the holding tank or other storage reservoir for a water source. For example, in some respects, a source of large amounts of fluid may be a holding tank or other storage reservoir that has a volume of about 37.85 hectoliters to about 757,082 hectoliters or more, preferably 37.85 hectoliters to about 454,349 hectoliters. In such an embodiment, the solutions of use of treated peracids provide a concentration of peracid (for example, peracetic acid) in the water source in volume from 0.1 ppm to about 100 ppm peracid or higher, preferably from about 1 ppm to about 100 ppm peracid or more. Without being limited according to the mechanism and / or scope of the invention, all ranges are included within the scope of the invention.
[0187] According to the various aspects of the invention, monitoring devices and / or means can be included to measure the rate of application and / or large amounts of peracid solution, in order to guarantee both the rate of peracid application (or the volume solution, with a maintained peracid) at a concentration of 0.1 ppm to about 100 ppm peracid or higher, preferably from about 1 ppm to about 100 ppm peracid or more.
[0188] In one aspect, treated peracid solutions can be added to dormant water sources. As one skilled in the art will find, the use of treated peracid solutions in dormant water sources will often require less frequent dosing than other water sources. For example, the use of treated water sources during periods of non-pumping (for example, non-use), such as, for example, winter will require less frequent dosing due to the more static nature of the water source at that particular time.
[0189] In an additional aspect, treated peracid solutions are added to waters that need treatment before disposal. In this respect, the recirculation waters (for example, post-fractionation) are treated to minimize microbial contamination in the waters and to remove solids prior to elimination of water in an underground well, reuse in a subsequent fracture application or return of water to local water sources. Such recirculating waters can be maintained, for example, in tanks, lakes or the like, in some aspects of the invention.
[0190] In one aspect, the water source that needs treatment can vary significantly. For example, the water source may be a source of drinking water (for example, reservoir water), salt water or a salt source, brackish water source, recycled water source, or the like. In one aspect, in which offshore well drilling operations are involved, salt water sources are often used (for example, salt water or non-salt water). Beneficially, the peroxide and peroxide reducing agent compositions of the invention, are suitable for use with any type of water and provide effective antimicrobial efficiency with any such water source.
[0191] Large volumes of water are used according to the invention, as required in fluid operations. As a result, in one aspect of the invention, recycled water sources (for example, production water) are often used to reduce the amount of potable water, tank water or seawater source needed. Recycled or production water is understood to include sources of non-potable water. The use of such produced waters (in combination with drinking water, reservoir water or sea water) reduces certain economic and / or environmental restrictions. In one aspect of the invention, thousands to millions of liters of water can be used and the combination of production-derived water with water sources provides significant economic and environmental advantages.
[0192] In one aspect of the invention, both production-derived and practical water is employed. In one embodiment, at least 1% of the water derived from production is used, preferably at least 5% of production water, preferably at least 10% of production water, preferably at least 20% of production water, or more preferably at least production water are employed. Without being limited according to the mechanism and / or scope of the invention, all ranges are included within the scope of the invention.
[0193] The source of treated water can comprise any suitable concentration of C1-C22 percarboxylic acid. In some embodiments, the source of treated water comprises from about 10 ppm to about 200 ppm of C1-C22 percarboxylic acid. In other embodiments, the source of treated water comprises about 1 ppm, 10 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm or 1,000 ppm percarboxylic acid C1-C22. 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, water derived from production and a combination of these. In some embodiments, the water source comprises at least about 1% by weight of water derived from production. 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 of water derived from production.
[0194] In one aspect of the invention, the method includes a pre-treatment step, in which the peracid composition is treated with a peroxide reducing agent to decrease the concentration of hydrogen peroxide in an in-use solution. The pretreatment step occurs before combining the antimicrobial composition of peracid and / or peroxide reducing agent with a water source that needs treatment. In one aspect of the invention, pretreatment can take place within a few minutes to hours before adding to a water source. Preferably, a commercial formulation of peracid is employed (for example, peracetic acid). After that, the solution for using the peroxide and peracid reducing agent composition can be diluted to obtain the desired peracetic acid concentrations, with low and / or no hydrogen peroxide concentration.
[0195] In accordance with embodiments of the invention, a sufficient amount of pre-treated peracid and the composition of the solution for use of the peroxide reducing agent are added to the aqueous water source in need of treatment to provide the desired peracid concentration for antimicrobial efficacy. For example, a source of water is dosed in quantities of the peroxide and peroxide reducing agent solution composition until a concentration of peptide in the water source is detected within the preferred concentration range (for example, about 1 ppm to about 100 ppm peracid). In one aspect, it is preferred to have a microbial count of less than about 100,000 microbes / ml, more preferably less than about 10,000 microbes / ml, or more preferably less than about 1,000 microbes / ml. Without being limited according to the mechanism and / or scope of the invention, all ranges are included within the scope of the invention.
[0196] In some modalities, 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, are killed, destroyed, removed and / or inactivated by the present methods. In another aspect of the invention, the method includes a step of pretreating the water source. In some aspects, the water source, which needs treatment, can be dosed first with an acidifier to lower the pH of the water source. Beneficially, in one aspect of the invention, pretreating a water source with an acidulant provides greater peracid stability in the water source.
[0197] The methods of use, as described in this document, may vary under temperature and pH conditions associated with the use of aqueous treatment fluids. For example, aqueous treatment fluids can be subjected to different ambient temperatures according to the applications of use described in this document, including those ranging from about 0 ° C to 180 ° C in the course of treatment operations. Preferably, the temperature range is between about 5 ° C to 100 ° C, more preferably between 10 ° C to about 80 ° C. Without being limited according to the mechanism and / or scope of the invention, all ranges are included within the scope of the invention. However, as most of the antimicrobial activity of the compositions of the invention occurs over a short period of time, exposure of the compositions to relatively high temperatures is not an important concern.
[0198] In addition, the aqueous treatment fluids of the peracid composition (i.e., use solutions) can be subjected to different pH ranges, such as from 1 to about 10.5. Preferably, the pH range is less than about 9, less than about 8.2 (pKa value of the peracid, representative peracetic acid) to ensure the effective antimicrobial efficacy of the peracid. In some aspects of the invention, a pH modifier (such as an acidulant) is added to a water source that needs treatment according to the invention. In some embodiments, it may be desirable to lower the pH to between about 5 and about 8.5. Without being limited according to the mechanism and / or scope of the invention, all ranges are included within the scope of the invention.
[0199] 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 that needs treatment for the occurrence of sufficient antimicrobial effect. The contact time may vary with the concentration of the compositions for use, the method of application of the compositions for use, the temperature of the compositions for use, the pH of the compositions for use, the amount of water to be treated, the amount of soil substrates or in the water to be treated, or the like. The contact or exposure time can be at least about 15 seconds. In some modalities, the exposure time is about 1 to 5 minutes. In other modalities, the exposure time is at least about 10 minutes, 30 minutes, or 60 minutes. In other modalities, the exposure time is from a few minutes to hours. In other modalities, the exposure time is a few days or more. Beneficially, the compositions for use according to the invention are suitable for short contact times, partly due to the non-oxidizing nature of the compositions having the hydrogen peroxide content reduced or eliminated. The contact time will also vary according to the peracid concentration in the solution used.
[0200] In other aspects of the invention, the methods include the direction of the treated water compositions in an underground environment and / or a well drilling. In some respects, treated water compositions are directed to an underground environment and / or well drilling, at a speed faster than about 3,577 liters / minute, 7,154 liters / minute faster than about and / or speed of about 7,750 liters / minute and about 11,924 liters / minute. Without being limited according to the mechanism and / or scope of the invention, all ranges are included within the scope of the invention. As noted in this document, an underground environment can include, for example, a shale gas reservoir, a well, and / or an oil reservoir. Beneficial Effects of Methods of Use on Water Treatment
[0201] In some respects, the methods revealed for the treatment of water in the recovery of oil and gas provide effective antimicrobial efficacy without harmful interaction with functional agents, including, for example, friction reducers. In an additional aspect, water treatment methods provide greater antimicrobial efficacy compared to the use of antimicrobial peracids alone. In an additional aspect, the methods of use result in the elimination 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 the peracid compositions minimizes the negative effects of the H2O2 oxidant.
[0202] In one aspect, the methods of use provide an antimicrobial agent for use that is not harmful to the environment. Beneficially, the degradation of the compositions of the invention provides a "green" alternative. In one aspect of the invention, the use of peracetic acid is beneficial as the by-products are non-toxic, do not persist in the environment, certified as organic and allowed for the discharge of surface water.
[0203] In an additional aspect, the methods of use provide an antimicrobial agent for use that does not interfere negatively with friction reducers, viscosity enhancers and / or other functional ingredients. In a further aspect, the methods of use do not negatively interfere with any additional functional agents used in water treatment methods, including, for example, corrosion inhibitors, anti-lime agents, and the like. The compositions administered according to the invention provide a very effective control of microorganisms, without adversely affecting the functional properties of any additive polymers in an aqueous system. In addition, solutions for using the treated peracid composition provide additional benefits to the system, including, for example, reduced corrosion within the system due to reduced hydrogen peroxide content or substantial decrease in a treated peracid composition.
[0204] Beneficially, the non-deleterious effects of treated peptide compositions (ie using a peroxide reducing agent) on the various functional ingredients used in water treatment methods are obtained regardless of the composition of the water source , which needs treatment.
[0205] In an additional aspect, the methods of use prevent contamination of systems, such as acidification of the reservoir or well. In other respects, the methods of use prevent microbiologically influenced corrosion of the systems in which they are employed.
[0206] In additional aspects of the invention, the reduction and / or elimination of hydrogen peroxide from the systems reduces the expansion of the volume within closed systems (for example, wells). As a result, there is a significantly reduced or eliminated risk of explosion from wells due to the removal of gases from within the antimicrobial compositions used to treat the various sources of water.
[0207] In other respects, the methods of use employ the antimicrobial and / or bleaching activity of 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, in a body or flow of water or a gas, or the like, by contacting the article, surface, body, or stream with the compositions. The contact may include any of several methods for applying the compositions, including, but not limited to, providing antimicrobial peracid compositions in an aqueous solution for use and immersing any articles, and / or to a source of water supply, that needs treatment.
[0208] The compositions are suitable for antimicrobial efficacy against a wide spectrum of microorganisms, providing a broad bactericidal spectrum and fungistatic activity. For example, the peracid biocides of the present invention provide broad spectrum activity against a wide variety of different types of microorganisms (including aerobic and anaerobic microorganisms), including bacteria, yeasts, molds, fungi, algae and other problematic microorganisms associated with operations of oil and gas fields.
[0209] Examples of microorganisms sensitive to the peracid compositions of this invention include, gram-positive bacteria (e.g., Staphylococus aureus, Bacillus species (sp.) Such as Bacillus subtilis, Clostridia sp.), Gram-negative bacteria (e.g. , Escherichia coli, Pseudomonas sp. Klebsiella pneumoniae, Legionella pneumophila, Enterobacter sp., Serratia sp., Desulfovibrio sp., And Desulfotomaculum sp.), Yeasts (eg Sacharomyces cerevisiae and Candi da albicans), fungi (eg Aspergus niger, Cephalosporium acremonium Penicillium notatum, and Aureobasidium pullulans), filamentous fungi (for example, Aspergillus niger and Cladosporium resine), algae (for example, Chlorella vulgaris, Euglena gracilis, and Selenastrum capricornutum), and other microorganisms (by microorganisms) phytoplankton and protozoa). Use in Other Treatments
[0210] Additional embodiments of the invention include water treatments for various industrial processes for the treatment of liquid systems. As used herein, "liquid system" refers to flood waters or an environment within at least one artificial device, containing a substantial amount of liquid that is capable of undergoing biological contamination. Liquid systems include, but are not limited to, liquid industrial systems, industrial water systems, liquid process streams, industrial process water systems, process water applications, process water, utility water, water used in manufacturing, water used in industrial services, aqueous liquid streams, liquid streams containing two or more liquid phases and any combination thereof.
[0211] In an additional aspect, the compositions and methods can also be used to treat other liquid systems where both the antimicrobial function of the compositions and oxidizing properties can be used. In addition to the microbial problems surrounding wastewater, wastewater is often rich in smelly sulfur, nitrogen or phosphorus-reducing compounds. A potent oxidizer, such as the compositions disclosed herein, efficiently convert these compounds into their odor-free derivatives, for example, sulfates, phosphates and amine oxides. These same properties are very useful in the pulp and paper industry, where the bleaching property is also very useful.
[0212] In an additional aspect, compositions and methods can also be used for various jobs in aseptic treatment. Description of various applications of use of peracid compositions treated with low or reduced hydrogen peroxide is provided for example in US Patent No. 8,226,939, entitled "Antimicrobial Peracid Compositions with Selected Catalase Enzymes and Methods of Use in Aseptic Packaging" incorporated as a reference in its entirety.
[0213] In one aspect, aseptic packaging charges, including the two categories: single use charge and reuse or recirculation charge are suitable for use in the compositions and methods of the invention. The simple-to-use system uses a diluted peracid solution. It sprays a small amount of this solution inside a package to sterilize it. The solution can be heated to the point of injection or it can be preheated before injection into the bottle. In both cases, the operating conditions (temperature, contact time and peracid concentration) are chosen so that the bottle becomes commercially sterile. After contact, inside the bottle, this spent solution is drained from the bottle and is exported by the load either to a drain or to other parts of the machine for environmental antimicrobial treatments or treatment of the outside of the bottles. After the bottle has been treated it will be rinsed with pure microbial water, filled with liquid food and sealed. All of these steps take place within a zone of positive pressure within the load called the sterile zone. In a reuse charge, the charge contains a reservoir of diluted peracid solution. This reservoir is maintained at the desired temperature (40-65 ° C). The cargo is drained from this reservoir and uses the solution to sterilize both the inside and outside of the bottles. The solution is drained from the bottles and is collected and exported back to the same reservoir from which it originates. After the bottle has been treated it is rinsed with microbiologically pure water, filled with liquid food and sealed. All of these steps occur within a zone of positive pressure within the load called a sterile zone.
[0214] In another aspect, the compositions and methods can be used in aseptic packaging, including contacting the container with a composition according to the present invention. Such contact can be obtained using a spray device or immersion tank or container to intimately contact the interior of the container with the composition for a period of time sufficient to clean or reduce the microbial population of the container. The container is then emptied of the amount of the present composition that has been used. After emptying, the container can then be washed with drinking water or sterile water (which may include a washing additive) and emptied again. After washing, the container can be filled with food. The container is then sealed, capped or closed and then packed for shipment for the final sale. Examples of containers that can be filled include polyethylene terephthalate (PET), high density polyethylene (HDPE), polypropylene (PP), low density polyethylene, polycarbonate (PC), polyvinyl alcohol (PVA), aluminum, simple films or multilayer or bags, paperboard, steel, glass, multilayer bottles, other type of polymeric packaging, the combination of these materials in films, bags, bottles or other food packaging materials.
[0215] Those skilled in the art will recognize, or be able to determine, using no more than routine experimentation, several equivalents for the specific procedures, modalities, claims and examples described in this document. Such equivalents are considered to be within the scope of that invention and covered by the appended claims. The content of all references, patents and patent applications cited throughout this application has been incorporated into this document as a reference to the same extent as if each individual publication or patent application was specifically and individually indicated as incorporated by reference. All publications and patent applications in this specification are indicative of the level of those versed in the technique to which this invention belongs. The invention is further illustrated by the following examples, which are not to be construed as further limiting. EXAMPLES
[0216] Modalities of the present invention are defined in more detail in the following non-limiting examples. It should be understood that these examples, while indicating certain embodiments of the invention, are provided by way of illustration only. From the discussion above and in these examples, one skilled in the art can determine the essential characteristics of that invention, and without departing from the spirit and scope of it, can make several changes and modifications to the modalities of the invention in order to adapt to various uses and conditions. Thus, various modifications of the modalities of the invention, in addition to those presented and described in this document, will be evident to those skilled in the art from the previous description. Such modifications are also within the scope of the appended claims. EXAMPLE 1
[0217] Corrosion tests were carried out. Corrosion rates were determined by a wheel box test, using bottles on a wheel in an oven. Each bottle contained a 1018 carbon steel coupon used for the analysis of weight loss after the test was completed. The test was carried out using water derived from production (for example, recycled water) from a gas / oil well and deionized water. The test was performed at room temperature and in triplicate. The average corrosion rates were compared with blank samples (no chemical added). PAA / H2O2 was administered in doses of 50, 300 and 900 ppm. The catalase was added at 1,000 ppm. The duration of the trial was 24 hours.
[0218] Results. The results of the corrosion tests for production-derived water and deionized water are shown in figure 1. For a sample of produced water, the addition of 1,000 ppm of catalase to the treatment with PAA / H2O2 decreased the corrosion rates of 1018 carbon steel approximately 30-50% (figure 1). In deionized water the reduction in the corrosion rate reached almost 60% (figure 2). EXAMPLE 2
[0219] An assessment of interference with reducing friction was conducted. Viscosity measurements were obtained using a FANN 35 Viscometer model. A total of 600 mL of tap water containing a friction reducer were treated with 200 ppm and 1,000 ppm peracetic acid, with and without catalase. The mixture was combined for 15 seconds with a Hamilton Beach hand mixer and the viscosity was measured at 300 rpm at room temperature. Viscosity values are reported in centipoise (cP).
[0220] Results. Table 1 shows the impact of PAA / H2O2 on friction reducers within a water source for oil / gas recovery, with and without the addition of catalase. A negative effect of PAA / H2O2 was observed in both friction reducers. However, the effect was reduced in all cases after treatment with catalase, indicating that the addition of catalase to remove H2O2 reduces any negative impact of PAA / H2O2 on friction reducers. TABLE 1

EXAMPLE 3
[0221] The impact of the water pretreatment with 500 ppm EnviroSan product (75 ppm POAA) was evaluated on the antimicrobial efficacy of various fractionation water mixtures. The example represents a baseline data set of the various water treatment options according to the invention. Table 2 and figure 3 illustrate the average log reduction in various fracture water treatments with different PAA ppm (without any catalase treatment or pretreatment), which represents a base data set. TABLE 2


[0222] Figure 3 shows the increasing amount of POAA needed in water samples tested with increased amount of water derived from production (reused water, for example). EXAMPLE 4
[0223] Studies for planktonic extermination were performed as an assessment of biocidal efficiency for PAA / H2O2 and applications of PAA / H2O2 / catalase. Briefly, water samples derived from production were used to test the efficiency of extermination of PAA / H2O2 in the following dosages: 25, 50, 75, 150 and 300 ppm of PAA. Catalase concentration was fixed at 1,000 ppm. The contact time was set to 10 and 60 minutes. After the contact time, bacterial enumeration was performed by means of an ATP quantification test. Enumeration of bacteria was calculated at the end of the appropriate time and the biocidal efficacy determined by comparison with an untreated sample.
[0224] Results. Planktonic extermination studies demonstrate that the addition of catalase increased the efficiency of microbial death (figures 4 and 5). For low dosage of PAA / H2O2 application (25 ppm), the addition of 1,000 ppm of catalase increased the biocidal efficiency by 48% after 10 minutes of treatment (23% after 60 minutes). The data in figures 4 and 5 are also shown in Tables 3A and 3B (respectively). TABLE 3A (contact 10 minutes)

TABLE 3B (60 minutes contact)
EXAMPLE 5
[0225] Additional biocidal test has been completed to assess the use of peracid and catalase compositions for water treatments used in oil fractionation. The use of approximately 15% by weight of commercially available EnviroSan (Ecolab, Inc., St. Paul, MN) peptide composition (POAA) with and without catalase was evaluated for the biocide's effectiveness in treating fractionation water of oil. An EnviroSan stock solution (about 1400 ppm POAA) with and without catalase was evaluated in particular.
[0226] EnviroSan solutions with catalase were prepared as follows: 1 g of EnviroSan (POAA) was added to 99 grams of deionized water in a beaker. One hundred milliliters of Optimase CA 400 L (catalase) was added with stirring via a syringe, and stirring continued for another 6.5 minutes. The subsequent test (QATM 317) indicates that the resulting solution contains ~ 1,400 ppm of peracetic acid, and no detectable H2O2. The stock solution of EnviroSan with catalase is stable for at least 30 minutes, with no detectable changes in the level of POAA and / or H2O2. A test system for Pseudomonas aeruginosa (ATC 15442) and bacterial populations of natural water was employed. P. aeruginosa were inoculated at room temperature (18 - 22 ° C) using tryptone glucose extract (TGE) agar plating media and incubated at 35 ° C for 48 hours.
[0227] Water mixtures, as described in Table 3A, were provided (showing the percentage of 100 mL of each type of water sample). The different substances under test and the amount of chemistry added to 10 ml of water from the inoculated sample to reach 20 ppm of residual POAA after 5 minutes inside the water mixture are shown in Table 4B. TABLE 4 A
* EnviroSan pretreated solutions with 300 ppm more than 24 hours before the micro-assessment TABLE 4B

[0228] Test methods. Before microtests (24 hours) mixtures of water C, E and G were combined and pretreated with 300 ppm EnviroSan. The water samples were dispensed in sterile 250 mL Erlenmeyer flasks according to Table 4A, ensuring that each flask contained 100 mL of total test water and mixed water types were completely homogeneous. Test water mixture was dispensed (24.75 ml) in a centrifuge tube and 0.25 ml of a 108 CFU / ml solution of P. aeruginosa culture was added and mixed thoroughly. 1 ml of inoculated water mixture was serially diluted in PBDW. Ten milliliters of the inoculated water mixture were distributed into two individual test tubes, in which the appropriate volume of EnviroSan solution with or without catalase (Table 4B) was added to achieve 20 ppm residual POAA for each test tube at time intervals and mixed. The methods of Example 5 were used to obtain EnviroSan with master catalase solutions. Then, samples of 1 mL neutralized in 9 mL of 0.5% sodium thiosulfate, were obtained after 2.5 minutes, as well as 5 minutes.
[0229] Results. Aerobic bacterial populations (CFU / mL) present in mixtures of water samples (either untreated or pretreated with 300 ppm EnviroSan) after inoculation with a culture of P. aeruginosa, as well as survivors present 2.5 minutes and 5 minutes after adding EnviroSan POAA + catalase were evaluated as shown in Table 5. TABLE 5





[0230] The average log reduction generated after a 2.5 minute exposure is shown (figure 6) at varying concentrations of POAA needed to reach 20 ppm residual POAA after 5 minutes in their respective fractionation water mix. In all tested fractionation water mixtures, there does not appear to be a consistent trend to indicate that there are significant differences in efficacy generated between treatment of mixtures with POAA vs POAA + catalase alone. The results indicate that there is no significant difference in the reduction of bacteria caused by the pre-treatment of water mixtures 24 hours before with 300 ppm of EnviroSan product, which demonstrates that the reduction of hydrogen peroxide with catalase does not negatively impact the effectiveness antimicrobial.
[0231] Without being limited to a theory of the invention, the dosage of POAA is likely to be high enough to generate significant extermination on its own, without the potential benefits of water pretreatment or EnviroSan pre-reduction by catalase. EXAMPLE 6
[0232] Additional microbial testing was conducted to assess whether fractionation waters treated with EnviroSan (POAA) pre-reduced with catalase (as shown in Example 5 showing significantly reduced consumption of POAA) result in improved antimicrobial efficacy. To assess improvements in antimicrobial efficacy, all water mixtures were treated with the same initial concentration of POAA EnviroSan (30 or 40 ppm) plus catalase, rather than targeting a residual level of POAA and adjusting the initial dosage accordingly. amount of present water produced.
[0233] The test systems (P. aeruginosa and natural water) described in Example 5 were used. Mixtures of water, as described in Table 6 were provided (showing the percentage of 100 mL of each type of water sample). TABLE 6

[0234] The water samples were dispensed in 250 mL Erlenmeyer flasks, sterile, according to Table 6, ensuring that each flask contained 100 mL of total test water and mixed water types were homogeneous. Fifty milliliters were saved for titration and 50 mL were used for the micro evaluation. Test water mixture was dispensed (24.75 ml) in a centrifuge tube and 0.25 ml of a 108 CFU / ml solution of P. aeruginosa culture was added and mixed thoroughly. 1 milliliter of inoculated water mixture was serially diluted in PBDW. Ten mL of the inoculated water mixture was distributed into two individual test tubes, in which the appropriate volume of the EnviroSan stock solution with catalase was added to achieve 30 ppm or 40 ppm POAA for each test tube at intervals of time and mixed. The methods of Example 5 were used to obtain EnviroSan with master catalase solutions. Then, 1 mL samples neutralized in 9 mL of 0.5% sodium thiosulfate, were obtained, after 2.5 minutes, as well as 5 minutes. Results: Table 7 shows the summary of the aerobic bacterial population (CFU / mL) present in mixtures of water samples before and after inoculation with a culture of Pseudomonas aeruginosa, as well as survivors present 2.5 minutes and 5 minutes after the addition 30 ppm or 40 ppm POAA + catalase. In addition, the bottom portion of the table summarizes the data for treating fresh water inoculated with 30 ppm and 40 ppm POAA alone as a comparator for those pre-reduced with catalase. TABLE 7




[0235] The titration data illustrates that the consumption of POAA was also analyzed and shown in Table 8. The titration data indicates that the addition of catalase to the test substance EnviroSan significantly reduces the rate of degradation of POAA within the water mixture , for 5 minutes, compared to the equivalent dosage of non-pre-reduced catalase chemistry. TABLE 8

[0236] The average log reduction generated after an exposure time of 2.5 minutes at 30 ppm or 40 ppm of EnviroSan POAA with or without catalase in different fractionation water mixtures is shown in Table 8 and Figure 7. A addition of catalase to the test substance EnviroSan appears to have no impact on the efficacy generated against organisms present in the inoculated fresh water samples. The data also suggest that with the increase in the amount of water derived from production in the tested water mixture, there is an increase in the efficiency generated within the exposure times of 2.5 and 5 minutes when treated with pre-reduced EnviroSan with catalase. EXAMPLE 7
[0237] Performance of additional antimicrobial efficacy was evaluated to confirm the improved antimicrobial efficacy observed in Example 6, when increasing amounts of production-derived water are used with the initial static dosage concentrations of POAA (30 ppm or 40 ppm) with catalase. The improved antimicrobial efficacy with increasing the amount of production water present in a mixture is a highly intuitive result and was unexpected. Under normal conditions, it would be expected to have decreased antimicrobial effectiveness as the amount of water derived from production (for example, recycled) increases and the amount of POAA remains static as a result of the increased contamination found in water derived from production, in opposed to water sources. As a result, the subsequent evaluation looked at the activity of the water itself, against a growing culture of Pseudomonas aeruginosa over an exposure period of 1 hour to determine whether the water derived from production itself has an antimicrobial presence.
[0238] All water mixtures were treated with an initial concentration of 30 ppm POAA EnviroSan, both with and without the addition of catalase. The data set assesses whether there is a significant difference in the microactivity generated between EnviroSan treatments alone vs. EnviroSan pre-reduced with catalase.
[0239] All proportions of fractionated water mixtures tested (100/0, 90/10, 80/20 and 70/30) were freshly mixed solutions as well as mixed and pre-treated solutions with 500 ppm of the EnviroSan product for more 1 hour before the start of the micro evaluation, in order to see if a pretreatment step is valuable for micro performance compared to untreated mixtures. The test system (P. aeruginosa and natural water) described in Example 5 was used again. Water mixtures, as described in Table 9, were provided (showing the percentage of 100 mL of each type of water sample). TABLE 9
* Solutions pretreated with 500 ppm EnviroSan for more than 1 hour before the micro evaluation.
[0240] The test methods of Example 5 were used for chemically treated water samples, differing only in the combination of 10 mL of inoculated water mixtures with appropriate volumes of EnviroSan with or without catalase to achieve 30 ppm residual POAA for each test tube at time intervals and mixed. The methods of Example 5 were used to obtain InviroSan with master catalase solutions. In comparison, for water samples that were not chemically treated, 9.9 ml of test water mixture was dispensed into two individual test tubes. 0.10 ml of an approximate value of 108 CFU / ml of P. aeruginosa culture was added at intervals of time and mixed very well. Then, 1 mL samples were neutralized in 9 mL of 0.5% sodium thiosulfate, followed by serial dilution and enumeration after exposure times of 2.5 minutes, 5 minutes and 60 minutes.
[0241] Table 10 shows a summary of the aerobic bacterial population (CFU / mL) present in water sample mixtures (either untreated or pretreated with 500 ppm EnviroSan) before and after inoculation with a culture of P aeruginosa, as well as survivors present 2.5 minutes and 5 minutes after the addition of 30 ppm POAA with or without catalase. In addition, the water sample count data for antimicrobial activity against P. aeruginosa in exposure for more than 60 minutes is also summarized in Table 10. TABLE 10






[0242] Water sample mixtures according to this study are summarized in Tables 11A-B, which show mixtures of water samples and chemical treatments (Table 10A) and the titrated concentrations of POAA (Table 11B). TABLE 11A
TABLE 11B

[0243] The titration data confirms that the addition of catalase to the test substance EnviroSan significantly reduces the rate of degradation of POAA in the water mixture for 5 minutes, compared to the equivalent dosage of the non-pre-reduced catalase chemistry. In addition, water pretreated with H2O2 1 hour before the test, slightly reduces degradation of POAA, thus, however, not as significantly as with the use of EnviroSan pre-reduced by catalase as the test substance.
[0244] Table 11C illustrates the use of 30 ppm POAA with / without catalase treatment compared to micro performance at both 2.5 and 5.0 minute exposure times. After adding 10-30% reuse water a definite drop in antimicrobial performance was observed over both 2.5 and 5 minutes while peracid was quickly consumed if not pre-treated with catalase. A residual of 30 ppm POAA at 5 minutes was required to achieve the desired antimicrobial performance. TABLE 11C

[0245] The data showed that, in the absence of reuse water (contaminated water) at 30 ppm POAA with / without catalase treatment, both achieved the desired antimicrobial performance. Figures 9 and 10, confirm the results of any difference in antimicrobial efficacy between water samples treated with 30 ppm POAA alone. 30 ppm of POAA + catalase for 2.5 minutes (figure 9) and 5 minutes (figure 10). It is believed that the use of fresh water does not interfere with the stability of POAA and, therefore, with the antimicrobial efficacy of POAA in fresh water solution.
[0246] The data confirm that there is a significant difference in the activity generated by POAA vs. POAA + catalase in tested water mixtures containing water derived from production. On average, there is at least a greater reduction of 2 log observed for samples treated with POAA + catalase, compared to samples treated with POAA only at the same time point (figure 11). This confirms the enhanced POAA stability and concomitant antimicrobial efficacy in reuse waters with reduced hydrogen peroxide content.
[0247] However, with the pretreatment of water mixtures with 500 ppm of EnviroSan for more than 1 hour before the test, the differences in effectiveness observed between treatments with POAA alone vs. POAA + catalase were eliminated (figure 12). The log survivors present 2.5, 5 and 60 minutes after adding a culture of P. aeruginosa in different mixtures of fractionation water were almost equivalent to the pretreatment at least one hour before the trial, thus confirming that water alone does not have antimicrobial properties. EXAMPLE 8
[0248] A comparison of the antimicrobial efficacy of POAA added in levels to obtain residual 30 ppm of POAA in 5 minutes versus catalase pretreated POAA was performed as set out in Table 12. TABLE 12

[0249] These data confirm that there is still an improvement in the antimicrobial efficacy of catalase-treated POAA, as opposed to POAA alone in all tested water mixtures containing at least 10% of production-derived water. (figure 13). This confirms the enhanced stability of POAA and the concomitant antimicrobial efficacy in reuse waters with reduced hydrogen peroxide content. EXAMPLE 9
[0250] The impact of the ratio of peracid to hydrogen peroxide on the stability of peracid in water derived from production was evaluated. Various commercially available solutions of peracid use have been used with ratios of peracid to hydrogen peroxide set out in Table 13. Figure 14 shows that the ratio of peracid to hydrogen peroxide improves peracid stability. TABLE 13

EXAMPLE 10
[0251] The effect of catalase on the stability of the peracid in the treated waters was evaluated. 80/20 water mixtures (80% fresh water / 20% production-derived water) were used to analyze the impact on various treatment sequences set out in Table 14. TABLE 14


[0252] As shown in figure 15, the most stable peracid systems were pretreated with the catalase prior to addition to the combined water sources. The use of 10x catalase yielded inferior results compared to the catalase pretreatment demonstrating a clear advantage for the pretreatment according to the invention, when using the combined compositions. The catalase-free composition demonstrated rapid degradation of POAA.
[0253] Due to the effective results shown in figure 15, the same methods were used to evaluate another pretreatment with a lower concentration of catalase, as illustrated in Table 15. TABLE 15

[0254] As shown in figure 16, the decrease in catalase used in the pretreated peracid composition again overcame the simultaneous addition of catalase to a peracid system and / or the catalase system. EXAMPLE 11
[0255] The antimicrobial efficacy of a 30 ppm composition of POAA (EnviroSan), 30 ppm of POAA (EnviroSan) with the catalase composition and a mixed composition of peracetic acid and 30 ppm peroctanoic acid (POAA / POOA) were compared (Figure 17). Antimicrobial efficacy was assessed using 80% fresh water / 20% of the water system derived from production from an oil and gas field operation. The mixed POAA / POOA composition demonstrated improvements over the use of the 30 ppm POAA-only composition. The same ppm of peracid provided significantly better results and, therefore, would allow the use in significantly lower doses, which demonstrates the synergy in a mixed peracid composition. EXAMPLE 12
[0256] The compatibility between peracetic acid and catalase compositions and components of gel fractionation fluids was evaluated. The changes in the viscosity of the gel fluid were evaluated by the addition of peracetic acid, with and without catalase. Linear guar pastes were initially prepared by hydrating guar polymers in a 5-speed Waring mixer. Deionized water was added and the mixture was stirred until a homogeneous mixture was obtained. The linear gels were cross-linked in the presence of cross-linked activators based on borate, and peracetic acid, with and without catalase. Fluid viscosity was subsequently monitored at 135 ° C for 200 minutes using a Grace 5500 rheometer with an R1B5 rotor-bob configuration.
[0257] The test pass / fail criteria were established as fluids maintaining a minimum viscosity of 200 cP for 120 minutes at 135 ° C. The results shown in figure 18 demonstrate that varying concentrations of peracetic acid, between 1 ppm and 1,000 ppm, together with different concentrations of catalase between 1 ppm and 200 ppm were tested. Figure 18 shows that the removal of hydrogen peroxide is critical for the viscosity of the gel to remain above 200 cP for as long as necessary. The excess of peracetic acid and hydrogen peroxide (for example, insufficient catalase) in a system did not manage to maintain the viscosity above 200 cP for the required time. The test cannot be performed with peracetic acid and hydrogen peroxide itself (ie, without catalase or other peroxide reducing agent) as the product prevented a gel from being formed. This is considered a failure and would not be compatible for use in the field. EXAMPLE 13
[0258] The concentration of the peracid compositions was evaluated to determine the ability to reduce the peroxide of the enzymes. The catalase enzyme was evaluated for effectiveness in reducing hydrogen peroxide in varying concentrations under increasingly increased peracid compositions. The commercially available Peracid Composition (POAA) EnviroSan (Ecolab, Inc., St. Paul, MN) was evaluated using the catalase enzymes added to the 2%, 3% and 5% peptide compositions. The catalase enzymes were added to the POAA solution and gently stirred under ambient conditions. After the addition of catalase, the stirring was stopped, and the samples were taken for iodometric testing.
[0259] As shown in Table 16, peroxide reducing enzymes have shown effectiveness in removing hydrogen peroxide from the peracid composition at peracid levels as high as 3% POAA; however, there was no impact at the 5% POAA level. TABLE 16

EXAMPLE 14
[0260] Different processes for forming reduced antimicrobial peroxide compositions according to the modalities of the invention were evaluated to determine the effects of the process on the peroxide reduction capacity of enzymes. A first process (A) combined a peracid composition with a solution containing the enzyme catalase. To 392 g of Dl water, 1.5 ml of ES 2000 catalase was added, then 107.37 g of the Peracid composition of EnviroSan (POAA) were slowly added to the solution over a period of 5 minutes, without stirring.
[0261] A second process (B) added a catalase composition to a diluted peracid composition. To the solution of 107.37 g of EnviroSan peptide composition (POAA) in 392 grams of deionized water, 0.5 ml of ES 2000 catalase was added over a period of 5 minutes, without stirring.
[0262] As shown in Table 17, the process of adding peroxide reducing enzymes impacted the hydroxide removal efficacy of the POAA peracid compositions. As shown in figure 19, the mixture of POAA and H2O2 is preferably added to the catalase solution to achieve maximum hydrogen peroxide removal / reduction efficiency. TABLE 17

EXAMPLE 15
[0263] Applications for use in the field have been analyzed to determine the amount of a peroxide reducing enzyme needed to obtain the desired concentrations of both peracid and hydrogen peroxide in a source of treated water. EnviroSan peracid composition (POAA) was added to the water to achieve the targeted concentrations shown in Table 18, and the concentration of both POAA and H2O2 was confirmed by iodometric titration. Then, the catalase (ES2000) was added to the solution, and the sample was stored under ambient conditions. The concentration of POAA and H2O2 was monitored by iodometric conditions.
[0264] As shown in Table 18, reservoir water with POAA and H2O2 can be treated with a minimum of 0.5 ppm catalase within 4 hours. The results further demonstrate that the higher levels (concentrations) of catalase work more efficiently in the decomposition of H2O2 from the peracid composition. Regardless, approximately 1 ppm of catalase is sufficient for the treatment of the water source. In addition, the results illustrate that, under tested ambient conditions, catalase selectively decomposes H2O2 without having any negative impact on the stability of POAA. TABLE 18

EXAMPLE 16
[0265] The stability of the peracid compositions treated according to the invention was evaluated to determine the impact of acidulants on the stability of the composition. The pH adjustments for the POAA compositions were performed using various acidulants to decrease the pH of the peracid compositions as a means of pretreating the compositions, before use according to the various methods of the present invention. The EnviroSan peracid composition (POAA) has been pre-treated with the following materials to assess the impact on the stability of POAA: chlorine dioxide (ClO2), catalase, or nitric acid (HNO3). The following methods were used to test the stability (measured by the remainder of ppm in POAA) of the peracid compositions in 20/80 water (derived from production / 5 grains of water), as set out in Table 19.
[0266] Chlorine dioxide (100 ppm) was added as a pretreatment with 100 mL of 100% production-derived water. Two hours passed before EnviroSan 1% was added and the stability of POAA was tested in the source of acidified water to be treated according to the invention.
[0267] Pretreatment consisted of adding 1% EnviroSan catalase to 100 ppm catalase. The solution was stirred for 6.5 minutes before the POAA stability was tested.
[0268] The pretreatment of 100 mL of 100% production-derived water with the acid (diluted HNO3 to pH 2.5) included stirring the solution magnetically for ~ 1 hour. Then, 20 g of acidified water to be treated according to the invention were mixed with 80 g of 5 grains of water, and the pH of the solution was adjusted from 5.5 to 6.6 before adding EnviroSan 1% to the POAA stability test.
[0269] No acidification and / or pretreatment of the water source was performed for the control experiment. TABLE 19
* Less interference observed in iodometric titration
[0270] As shown in figure 20, there is a clear advantage to the use of an acidulant with the peracid compositions treated according to the invention, in order to improve the stability of the peracid. The improved stability (ppm of AOPA over time) demonstrates that a pretreatment of a water source to lower the pH of the water to be acidic, results in prolonged peracid stability. EXAMPLE 17
[0271] To a mixture of 80/20 water (produced water / 5 grains) several peracid compositions were added, with stirring. The level of peracid at specific times was determined by iodometric titration. The following peracid compositions were used: EnviroSan: 60 milliliters / 100 g (POAA, 13.97%, H2O2, 10.41%); POAA with low Peroxide content: 65 milliliters / 100 g (POAA 12.72, H2O2, 1.55%); and EnviroSan / HAC (ie acidified EnviroSan): 60 milliliters EnviroSan plus 25 milliliters / Hac / 100 g.
[0272] For the catalase treatment, 0.3 g of ES 2000 was added to 78.53 g of water, then 21.47 g of EnviroSan was added to the solution, without stirring. At the end of the addition, the concentrations of peracid and hydrogen peroxide were tested (POAA 2.77%, H2O2 20.51%). The results are shown in Table 20. TABLE 20


[0273] Again, as shown in figure 21, there is a clear advantage to the use of an acidulant, with the peracid compositions treated according to the invention, in order to improve the stability of the peracid. EXAMPLE 18
[0274] An inorganic metal peroxide reducing agent has been evaluated for its specificity of reducing hydrogen peroxide in peptide compositions, compared to peracid reduction. As shown in Table 21, several POAA compositions with varying concentrations from hydrogen peroxide were contacted with a platinum (Pt) catalyst.
[0275] The tested compositions were generated as follows: Composition A (2,000 ppm POAA plus 250 ppm H2O2; 0.2166% weight / weight of peracid, 0.0034% by weight of measured H2O2); Composition B (2,000 ppm of POAA with 500 ppm H2O2; 0.2166% weight / weight of peracid, 0.0094% by weight of measured H2O2); Composition C (2,000 ppm of POAA more than 1,000 ppm H2O2; 0.2138% weight / weight of peracid, 0.0340% weight of measured H2O2); Composition D (2,000 ppm of POAA and 2,000 ppm of H2O2; 0.2119% weight / weight of peracid, 0.0540% by weight of measured H2O2).
[0276] A zeolite (ie, a porous structure that can accommodate a wide variety of cations and which are used in the catalyst formulation) was used to suspend a sample of an inorganic metal peroxide reducing agent. The zeolite was saturated with various metal peroxide reducing agents (as set out in the various different examples) in a solution of peracetic acid. The zeolites that have been used are commonly used in the hydrocarbon cracking industry for catalysis. The concentrations of POAA and H2O2 were then measured, with an iodometric titration over time to show the impact of the particular metal peroxide reducing agent on the selective or non-selective degradation of POAA and / or H2O2.
[0277] Table 21 shows the comparison of the initial POAA concentration and the final POAA concentration after 15 minutes of contact with the peroxide reducing agent, according to the invention this is illustrated in figure 22. TABLE 21


[0278] As shown in Table 22, the decomposition rates of the concentration of POAA in the various peracid compositions are shown in addition. As shown in Table 22, and in Figure 23, as the concentration of hydrogen peroxide increases, the loss rate of AOPA increases in a similar way. As a result, the peroxide reducing agent provides a partially selective peroxide decomposition of the peracid compositions. TABLE 22

[0279] The results demonstrate the partial selectivity of the platinum inorganic peroxide (Pt) reducing agent suitable for use according to the methods of the invention. The inorganic peroxide reducing agent was then evaluated in combination with the peroxide reducing catalase enzyme. The 2,000 ppm POAA compositions were measured at 0 minutes, 30 minutes, 60 minutes, 120 minutes and 240 minutes, as shown in Table 23, according to the various combinations with a peroxide-reducing catalase enzyme. TABLE 23


[0280] Figure 24 graphically shows the results of the reduction in POAA (eg, peracid decomposition), which shows that the inorganic peroxide reducing agent results in less selective hydrogen peroxide loss or decomposition compared to the enzyme peroxide-reducing catalase. However, the inorganic peroxide reducing agent provides a partially selective peroxide decomposition of the peracid compositions. EXAMPLE 19
[0281] Additional inorganic metals were evaluated for use as solid catalysts for evaluation as peroxide decomposition catalysts according to the methods of the invention. The metals tungsten (W), zirconium (Zr) and ruthenium (Ru), were evaluated to determine whether the metals preferentially reduce the concentration of hydrogen peroxide in relation to the concentration of peracid within a peracid composition. Table 24 shows the various formulations evaluated over 4 hours. TABLE 24

[0282] As shown in figure 25 the decrease in both AOPA (eg, peracid decomposition) and hydrogen peroxide is compared. Both inorganic peroxide reducing agents resulted in a significant decrease in both POAA and hydrogen peroxide, showing only a slight preference in the decomposition of hydrogen peroxide in relation to POAA. EXAMPLE 20
[0283] Various additional inorganic metals and metallic compounds have been further evaluated for use as peroxide decomposition catalysts (e.g., peroxide reducing agents) according to the methods of the invention. The metals were supplied as solid catalysts for POAA solutions.
[0284] Table 25 shows the various solutions that were tested against 10 g of CoMo, sample of cobalt molybdenum peroxide reducing agent including a POAA plus peracid catalase composition, hydrogen peroxide, more acetic acid composition, peroxide composition hydrogen. TABLE 25

[0285] As shown in figures 26-27, the loss of POAA (figure 26) and the loss of hydrogen peroxide (figure 27) are a function of the time of exposure to the peroxide reducing agent CoMo. Table 26 shows the various solutions that were tested against 10 g of NiW, a sample of inorganic nickel tungsten peroxide reducing agent, including a POAA plus catalase peracid composition plus acetic acid composition, hydrogen peroxide composition. TABLE 26

[0286] As shown in figures 28-29 the loss of POAA (figure 28) and the loss of hydrogen peroxide (figure 29) are a function of time in the presence of a NiW peroxide reducing agent.
[0287] Table 27 shows the various solutions that were tested against 10 g of NiMo, a sample of nickel molybdenum inorganic peroxide reducing agent, including a POAA plus peroxide catalase composition, hydrogen peroxide composition plus acetic acid and hydrogen peroxide composition. TABLE 27


[0288] As shown in figures 30-31 the POAA loss (figure 30) and the loss of hydrogen peroxide (figure 31) are a function of time in the presence of a NiMo peroxide reducing agent.
[0289] Additional tests using NiMo, nickel inorganic-nicomolibdenum reducing agent nickel were performed using a different titration methodology, due to some molybdenum metal bleach in the POAA solution (for example, with potentially negative effects on peroxide separation POAA / hydrogen). To correct this, two separate 10 mL samples were collected at each time point during the test. One of the samples was treated with a small amount (~ 1 mmL) of catalase added to eliminate hydrogen peroxide in the solution. The second solution was titrated to the total oxygen content, with the addition of oxygen catalyst, sulfuric acid and KI. As a result, the volume of titration in the sample treated with catalase represents a direct measurement of the content of POAA in the solution, and the total titration of oxygen, less the titration treated with catalase is equal to the amount of peroxide in the solution. The results are described in Table 28 and shown in figures 32-33. TABLE 28A

TABLE 28B (POAA pretreated with catalase)

[0290] Table 29 shows the various solutions that were tested against 10 g of Mo, a sample of inorganic molybdenum peroxide reducing agent, including a composition of POAA plus peracid catalase, composition of hydrogen peroxide plus acetic acid, composition of hydrogen peroxide. TABLE 29


[0291] As shown in figures 34-35 the POAA loss (figure 34) and the loss of hydrogen peroxide (figure 35) are a function of time in the presence of a Mo peroxide reducing agent.
[0292] Additional tests using the Mo, inorganic peroxide-reducing agent comolibdenum were carried out using a different methodology from the titration, as described above with respect to the NiMo catalyst test that was reanalyzed. The results are described in Table 30 and shown in Figures 3637. TABLE 30A
TABLE 30B (POAA pretreated with catalase)
EXAMPLE 21
[0293] The antimicrobial efficacy of peracid compositions, using various peroxide reducing agents according to the modalities of the invention was analyzed, as illustrated in Table 31. The control sample was a source of contaminated water from a composition of field water used in the field for hydraulic fracturing (ie, 73.412.793.2 micro equivalents per gram of contaminants). Samples of peracids with and without hypochlorite were added to the source of contaminated control water and were tested to determine the effect on the antimicrobial efficacy of the use and sequencing of the potential peroxide reducing agent. As a reference, in this example, the POAA used is a 15% peracetic acid and 10% hydrogen peroxide composition (as commercially available as EnviroSan). As set out in Tables 31-32, "X2" refers to a second dosing sequence at POAA and / or hypochlorite for the control contaminated water source. For example, a first 250 ppm dose of POAA was added to treat the source of contaminated control water and then a second dose was administered.
[0294] According to Tables 31-32, the amount of active (ppm) POAA and / or hypochlorite in the control of treated water sources is as follows, for example: 250 ppm of POAA is equivalent to 37.5 ppm of POAA in solution from the control water source; 250 ppm of hydrogen peroxide is equivalent to 25 ppm of hydrogen peroxide in the control water source solution. TABLE 31


[0295] The additional assessment of the process of using peroxide reducing agents in sequence was further analyzed as shown in Table 32, using additional water samples, including deionized (ie, uncontaminated) water and control (as defined above as contaminated water source). TABLE 32




[0296] The results presented in Table 32 demonstrate that the hypochlorite has an effective impact on the decomposition of hydrogen peroxide (in water containing no biological contamination). Mixed systems showed an increase in peroxide decomposition compared to unmixed peracid systems. This demonstrates the effect of biological contamination on water competing with the deterioration of hydrogen peroxide by sodium hypochlorite. The faster decomposition or fall of sodium hypochlorite and peracetic acid is observed in conjunction with an increase in the percentage of microbial reduction while hydrogen peroxide shows increased stability.
[0297] Peracetic acid and sodium hypochlorite are indistinguishable in titration, and are therefore presumed to consist of half of the titratable material; however, the focus of the assessment was exclusively on the decomposition of hydrogen peroxide. EXAMPLE 22
[0298] An application for use in the field was analyzed to determine the effectiveness of the peroxide-reducing catalase enzyme in reservoir water under ambient conditions. Catalase (ES 2000) was used in a reservoir water source (441,189.74 hectoliters) to reduce / eliminate H2O2 in a POAA peracid composition. The water in the reservoir, when sampled, contained both POAA and H2O2. The treatments analyzed were based on established laboratory data, in which, at 1 ppm, the level of use selectivity reduced the H2O2 to zero in about 4 hours. An initial catalase treatment in the reservoir water applied in the late morning under clear climatic conditions and ambient outdoor temperatures in the range of 32.22 ° C (+) did not result in any significant elimination of hydrogen peroxide as expected. Thus, samples of 100 grams of water from the reservoir were used to add various levels of 1 ppm catalase (Table 33) or 2 ppm catalase (Table 34).
[0299] The samples were then stored under several identified conditions: room temperature, outside in sunlight, outside protected from sunlight. The level of hydrogen peroxide was tested at various times (shown at 0 hours and 2 hours) to verify the functionality of the catalase peroxide reducing agent. As mentioned in the tables, the following measures are defined as follows: EP1 V (mL 0.05 N Na2S2O3) and EP2 V (mL 0.05 N Na2S2O3).
[0300] As shown in Tables 33-34, light has a significant negative impact on the performance of the catalase enzyme in reducing the concentration of H2O2 from the peracid composition. The results further demonstrate that the temperature under the investigated conditions has a positive impact on the functionality of the catalase. TABLE 33

TABLE 34

[0301] The results of the field tests demonstrate usefulness for the inclusion of a UV blocking agent in certain applications of use of the peroxide reducing agent, that is, a peroxide reducing enzyme, such as catalase. A UV blocking agent can alternatively be replaced with application methods that minimize exposure to sunlight (for example, dosing the peroxide reducing agent at a time, without and / or in poor sunlight, such as during night and / or cloudy periods). In still other aspects, field trials demonstrate applications of use suitable for the use of a dye, such as a UV blocking agent to prevent sunlight from entering a water system that requires treatment with the UV blocking agent for the effective reduction of hydrogen peroxide according to the invention.
[0302] The invention being thus described, it is clear that it can vary in many ways. Such variations should not be considered as departing from the spirit and scope of the invention and all such modifications are intended to be included in the scope of the following claims.

权利要求:
Claims (30)
[0001]
1. Method of treating water sources for oil or gas operation CHARACTERIZED by the fact that it comprises: a first step of any treatment of a percarboxylic acid composition with an inorganic peroxide reducing agent to generate an antimicrobial composition or addition of an percarboxylic acid and peroxide reducing agent to an oil or gas operating water source that needs treatment; form a source of treated water, wherein the source of treated water comprises (i) up to 1,000 ppm of inorganic peroxide reducing agent, wherein said agent is a hypohalide or a catalase enzyme, (ii) substantially free of peroxide hydrogen; (iii) from 0.0001% by weight to 10.0% by weight of a C1-C22 carboxylic acid; and (iv) from 0.0001% by weight to 10.0% by weight of a C1-C22 percarboxylic acid; wherein the peroxide reducing agent reduces and / or eliminates hydrogen peroxide from the percaboxylic acid composition; where the water source in need of treatment comprises fresh water, reservoir water, sea water, drilling fluid water, hydraulic fracturing water, production-derived water comprising recycled and / or non-potable water, or a combination of them from an oil and gas operation; and direct the source of treated water in an underground environment or disposal of the source of treated water with a minimized environmental impact.
[0002]
2. Method, according to claim 1, CHARACTERIZED by the fact that the source of water that needs treatment is water derived from production.
[0003]
3. Method, according to claim 2, CHARACTERIZED by the fact that the water source is at least 1% by weight of the water derived from production and in which the antimicrobial effectiveness of the antimicrobial composition of the treated water source is superior to antimicrobial effects of a water source that does not contain water derived from production.
[0004]
4. Method, according to claim 1, CHARACTERIZED by the fact that the treatment of the percarboxylic acid composition with the peroxide reducing agent to generate the antimicrobial composition is not a pre-treatment step and occurs at the water source, which needs treatment.
[0005]
5. Method, according to claim 1, CHARACTERIZED by the fact that treated water reduces corrosion caused by hydrogen peroxide and reduces induced microbial corrosion, and in that the antimicrobial composition does not interfere with friction reducers, viscosity enhancers , other functional ingredients found in the water source, or combinations thereof.
[0006]
6. Method according to claim 1, CHARACTERIZED by the fact that the stability of percarboxylic acid is improved through the pre-treatment step to minimize the concentration of hydrogen peroxide in the percarboxylic acid composition to be substantially free of peroxide peroxide. hydrogen, and where the concentration of C1-C22 carboxylic acid is from 0.0001% by weight to 5.0% by weight, and where the concentration of C1-C22 percarboxylic acid is from 0.0001% by weight to 5% , 0% by weight.
[0007]
7. Method according to claim 1, CHARACTERIZED by the fact that percarboxylic acid is peracetic acid and carboxylic acid is acetic acid.
[0008]
8. Method, according to claim 1, CHARACTERIZED by the fact that the acidulant is added to the water source in need of treatment, before adding the antimicrobial composition to a water source.
[0009]
9. Method according to claim 1, CHARACTERIZED by the fact that the antimicrobial composition and / or the treated water source further comprises a UV blocking agent.
[0010]
10. Method, according to claim 9, CHARACTERIZED by the fact that the UV blocking agent is a natural or synthetic dye, and the water source, which needs treatment, is selected from the group consisting of fresh water, drinking water reservoir, sea water, water derived from production and combinations thereof.
[0011]
11. Method according to claim 9, CHARACTERIZED by the fact that the UV blocking agent is a cationic dye, and in which the water source is at least 1% by weight of the water derived from production and in which the The antimicrobial effectiveness of the antimicrobial composition on the treated water source is superior to the antimicrobial effects of a water source that does not contain production-derived water.
[0012]
12. Method according to claim 9, CHARACTERIZED by the fact that the UV blocking agent is methylene blue.
[0013]
13. Method, according to claim 1, CHARACTERIZED by the fact that the source of treated water reduces corrosion caused by hydrogen peroxide and reduces induced microbial corrosion, and in that the antimicrobial composition does not interfere with friction reducers , viscosity enhancers, other functional ingredients found in the water source or in their combinations.
[0014]
14. Method, according to claim 13, CHARACTERIZED by the fact that the water source is fresh water, reservoir water, sea water, water derived from production, or combinations thereof.
[0015]
15. Method, according to claim 14, CHARACTERIZED by the fact that said antimicrobial composition provides superior antimicrobial efficacy compared to a water source that does not contain water derived from production.
[0016]
16. Method according to claim 13, CHARACTERIZED by the fact that the stability of percarboxylic acid is improved by reducing the concentration of hydrogen peroxide as a result of the addition of the peroxide reducing agent.
[0017]
17. Method according to claim 13, CHARACTERIZED by the fact that percarboxylic acid is peracetic acid and carboxylic acid is acetic acid.
[0018]
18. Method according to claim 13, CHARACTERIZED by the fact that the addition of the percarboxylic acid composition and the peroxide reducing agent to the water source occurs in each dosing cycle of at least 5 days.
[0019]
19. Method, according to claim 13, CHARACTERIZED by the fact that the acidulant is added to the water source that needs treatment, before the addition of percarboxylic acid and peroxide reducing agent to the water source.
[0020]
20. Method according to claim 13, CHARACTERIZED by the fact that the antimicrobial composition and / or the treated water source additionally comprise a UV blocking agent.
[0021]
21. Method, according to claim 20, CHARACTERIZED by the fact that the UV blocking agent is a natural or synthetic dye, and in which the water source, which needs treatment, is selected from the group consisting of fresh water, reservoir water, sea water, water derived from production and combinations thereof.
[0022]
22. Method according to claim 20, CHARACTERIZED by the fact that the UV blocking agent is a cationic dye, and in which the water source is at least 1% by weight of the water derived from production and in which the effectiveness The antimicrobial composition of the antimicrobial composition in the treated water source is superior to the antimicrobial effects of a water source that does not contain water derived from production.
[0023]
23. Method according to claim 20, CHARACTERIZED by the fact that the UV blocking agent is methylene blue.
[0024]
24. Method, according to claim 1, CHARACTERIZED by the fact that the inorganic peroxide reducing agent is a hypohalide.
[0025]
25. Aqueous water treatment composition with antimicrobial activity, as defined in claim 1, CHARACTERIZED by the fact that it comprises: a water source derived from the production of a water source for oil and gas operation; from 1 ppm to 1,000 ppm of a peroxide reducing enzyme, where the enzyme is a catalase enzyme; substantially free of hydrogen peroxide; from 0.0001% by weight to 10.0% by weight of a C1-C22 carboxylic acid; and from 0.0001% by weight to 10.0% by weight of a C1-C22 percarboxylic acid, in which the aqueous water treatment composition does not interfere with friction reducers, viscosity enhancers, other functional ingredients found in the source of water or combinations thereof.
[0026]
26. Composition according to claim 25, CHARACTERIZED by the fact that it additionally comprises at least one polymer or copolymer for modifying the fluid viscosity, reducing friction and / or inhibiting corrosion, in which the catalase does not interfere negatively with the activity of one or more polymer (s) or copolymer (s), and where the pH is less than 9.
[0027]
27. Composition according to claim 25, CHARACTERIZED by the fact that percarboxylic acid is peracetic acid and in which carboxylic acid is acetic acid, and in which the source of water derived from production is at least 1% by weight of the composition.
[0028]
28. Composition, according to claim 25, CHARACTERIZED by the fact that the source of water produced is a source of fracturing water.
[0029]
29. Composition according to claim 25, CHARACTERIZED by the fact that the peracid is selected from the group consisting of a peracetic acid, a peroxioctanoic acid, a sulfoperoxycarboxylic acid, a peroxisulfonated oleic acid and combinations thereof.
[0030]
30. Composition according to claim 25, CHARACTERIZED by the fact that it additionally comprises a stabilizing agent and in which the pH is less than 9.

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同族专利:

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公开号 | 公开日

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CA2867565C|2021-01-19|

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US20130264293A1|2013-10-10|

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US20130259743A1|2013-10-03|

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EP2831000A1|2015-02-04|

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CN104254496A|2014-12-31|

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AU2013240312B2|2017-08-03|

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CN104254496B|2016-10-26|

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WO2013148200A1|2013-10-03|

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CA2867565A1|2013-10-03|

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AU2013240312C1|2018-02-01|

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MX2014011189A|2014-10-06|

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CN106396037B|2019-10-15|

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US9926214B2|2018-03-27|

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AU2013240312A1|2014-08-21|

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US20160137535A1|2016-05-19|

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ECSP14023313A|2015-09-30|

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US10017403B2|2018-07-10|

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EP2831000A4|2016-03-30|

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US20130264059A1|2013-10-10|

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US10023484B2|2018-07-17|

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US9242879B2|2016-01-26|

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CN106396037A|2017-02-15|

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MX360142B|2018-10-24|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-09-03| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-07-21| B07A| Technical examination (opinion): publication of technical examination (opinion)|

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2020-12-15| B09A| Decision: intention to grant|

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2021-02-23| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/03/2013, 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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US201261617814P| true| 2012-03-30|2012-03-30|

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US6/617,814|2012-03-30|

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PCT/US2013/030904|WO2013148200A1|2012-03-30|2013-03-13|Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water|

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