WO2018085235A1

WO2018085235A1 - Stabilization of super-activated peroxy compounds

Info

Publication number: WO2018085235A1
Application number: PCT/US2017/059216
Authority: WO
Inventors: Thomas I. Marks
Original assignee: Marks Thomas I
Priority date: 2016-11-01
Filing date: 2017-10-31
Publication date: 2018-05-11

Abstract

Super-activated peroxy compounds are subject to rapid deactivation by naturally formed and occurring catalase enzyme, making their use commercially non-viable. Stabilization of acid-deformed catalase with specially selected bridging compounds establish stable bridges that prevent the reverse reaction back to the enzyme's active state. This stabilized deformation of the catalase enzyme leads to stabilized super-activated peroxy compounds, as they are not enzymatically degraded before their use as oxidants.

Description

STABILIZATION OF SUPER-ACTIVATED PEROXY COMPOUNDS

[0001] This application claims benefit of and priority to U.S. Provisional Application No. 62/415,901, filed November 1, 2016 by Thomas I. Marks, and is entitled to the benefit of that filing date. The entire disclosure of U.S. Provisional Application No. 62/415,901 is incorporated herein by specific reference for all purposes.

TECHNICAL FIELD

[0002] The presently disclosed subject matter relates to a composition including at least one super- activated peroxy compound and at least one stabilizing bridging compound. The presently disclosed subject matter further relates to a method for preparation of the stabilized super-activated peroxy compounds, and a method for applications in industries such as potable water treatment, cooling water treatment, wastewater treatment, electronic component manufacturing, pharmaceutical manufacturing, pulp and paper industry, food processing, and downhole and downstream applications in the oil and gas industry.

SUMMARY

[0003] The presently-disclosed subject matter meets some or all of the above-identified needs, as will become evident to those of ordinary skill in the art after a study of information provided in this document. This disclosure describes several embodiments of the presently-disclosed subject matter, and in many cases lists variations and permutations of these embodiments. This disclosure is merely exemplary of the numerous and varied embodiments. Mention of one or more representative features of a given embodiment is likewise exemplary. Such an embodiment can typically exist with or without the feature(s) mentioned; likewise, those features can be applied to other embodiments of the presently-disclosed subject matter, whether listed in this disclosure or not. To avoid excessive repetition, this disclosure does not list or suggest all possible combinations of such features.

[0004] In some embodiments, the presently disclosed subject matter relates to a composition. The composition includes one or more super-activated peroxy compounds with one or more bridging compounds. In some embodiments, the super-activated peroxy compound includes a blend of one or more strong acids. Non-limiting examples of the strong acids include hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, or the corresponding partial salts thereof, including sodium, potassium, calcium, magnesium, and aluminum, and one or more peroxy compounds selected from a group comprising inorganic peroxides and organic peroxides, hydrogen peroxide, perborates, percarbonates, persulfates, perphosphates, and combinations thereof. In some embodiments, the one or more bridging compounds includes an organic acid or blend thereof that can be non-polar in acid conditions. In some embodiments, the organic acid is polyprotic. Non-limiting examples of the organic acid includes citric, malic, formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, undecanoic, dodecanoic, lactic, maleic, ascorbic, hydroxyacetic, neopentanoic, neoheptanoic, neodecanoic, oxalic, malonic, succinic, glutaric, adipic, pimelic, and subric acid, and salts thereof. In some embodiments, the salt of the organic acid includes non-limiting examples of sodium, potassium, calcium, magnesium, and aluminum, and phosphoric acid. In some embodiments, the one or more bridging compound includes an organo-carboxylic acid with additional functional groups. Non-limiting examples include hydroxyls, additional carboxylic groups, chlorides, sulfates, unsaturation, phosphates, wherein the organo-carboxylic is in undissociated acid form or salts thereof. In one embodiment, the one or more bridging compound is a citric acid. In some embodiments, the citric acid provides the optimal structural bridge to stabilize the deformed catalase. In some embodiments, the citric acid provides additional functional reactivity with contaminants comprising calcium, magnesium, and iron salts. In some embodiments, the bridging compound stabilizes acid-deformed catalase enzyme by bridging of the deformed structure. In some embodiments, the stabilization of the deformed catalase provides stabilization of a super-activated peroxy compound by limiting its destruction through enzymatic breakdown by active catalase. In some embodiments, the one or more bridging compounds is in liquid or solid form. In some embodiments, the one or more bridging compounds is about 0.1% to about 100% percent active. In some embodiments, wherein the ratio of bridging compound to super-activated peroxy compound is 1 : 1000 to 1000: 1. In some embodiments, the ratio of bridging compound to super-activated peroxy compound is adjusted for additional contaminant demand from the baseline conditions of the system prior to addition of the bridging compound and super-activated peroxy compound. In some embodiments, the bridging compound is blended with the super-activated peroxy compound in a shipping container by separate addition or simultaneous addition.

[0005] In some embodiments of the presently disclosed subject matter, the one or more bridging compound in the composition is added before, during, or after preparation of the super-activated peroxy compound. In some embodiments, wherein the blend of bridging compound and super-activated peroxy compound is prepared on-site, at the point of application, in-line prior to the application, or off-site at a manufacturing location.

[0006] In further embodiments, the blend of bridging compound and super-activated peroxy compound is prepared into a formulation, and the formulation is a stabilized super-activated peroxy compound. In some embodiments, the formulation further includes other functional additives. Non-limiting examples include product stabilizers, acids and acid blends, alkalis and alkali blends, deposit control agents, cleaning formulations and surfactants, thickening agents, foaming agents, defoamers, solvents, scale control agents, corrosion inhibitors, and biocides.

[0007] In some embodiments, the composition is applied in combination with other functional additives, including acids and acid blends, alkalis and alkali blends, deposit control agents, cleaning formulations and surfactants, thickening agents, foaming agents, defoamers, solvents, scale control agents, corrosion inhibitors, and biocides.

[0008] In some embodiments, the stabilized super-activated peroxy compound is used in an industrial processes to cost-effectively produce a targeted oxidizing reaction, including breaking down toxic and corrosive sulfides in processing waters of the oilfield and wastewater, destroying taste and odor contaminants in potable and drinking water, eliminating organic foulants such as paraffins and naphthenics in the oilfield and process contaminants in cooling water, removal of destructive contaminants from processing waters in the electronics and pharmaceutical industries, destruction of fouling biofilm in processing and cooling waters, or elimination of hazardous pollutants in wastewater.

[0009] In another aspect, the presently disclosed subject matter relates to a method of stabilizing the super-activated peroxy compound, which includes preparing one or more super-activated peroxy compound by mixing at least one strong acid with at least one peroxy compound, and adding one or more bridging compounds. In some embodiments, the one or more bridging compound is added before, during, or after preparation of the super-activated peroxy compound. In some embodiments, the blend of bridging compound and super-activated peroxy compound is prepared on-site, at the point of application, in-line prior to the application, or off-site at a manufacturing location.

[00010] In some embodiments, the method further includes the step of adding at least one functional additive. Non-limiting examples of the additive include product stabilizers, acids and acid blends, alkalis and alkali blends, deposit control agents, cleaning formulations and surfactants, thickening agents, foaming agents, defoamers, solvents, scale control agents, corrosion inhibitors, or biocides. In some embodiments, the ratio of bridging compound to super-activated peroxy compound is 1: 1000 to 1000: 1. In some embodiments, the bridging compound is added with the super-activated peroxy compound in a shipping container by separate addition or simultaneous addition.

[00011] In some embodiments, the presently related subject matter relates to a method of treating water flows, which includes adding the stabilized, super-activated peroxy compound to water flows. In some embodiments, the water flows can be reused. In some embodiments, the water flow treated with stabilized super-activated peroxy compound is used in an industrial process to cost-effectively produce a targeted oxidizing reaction. In some embodiments, the industrial process comprising breaking down toxic and corrosive sulfides in processing waters of the oilfield and wastewater, destroying taste and odor contaminants in potable and drinking water, eliminating organic foulants such as paraffins and naphthenics in the oilfield and process contaminants in cooling water, removal of destructive contaminants from processing waters in the electronics and pharmaceutical industries, destruction of fouling biofilm in processing and cooling waters, or elimination of hazardous pollutants in wastewater. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

[00012] The details of one or more embodiments of the presently-disclosed subject matter are set forth in this document. Modifications to embodiments described in this document, and other embodiments, will be evident to those of ordinary skill in the art after a study of the information provided in this document. The information provided in this document, and particularly the specific details of the described exemplary embodiments, is provided primarily for clearness of understanding and no unnecessary limitations are to be understood therefrom. In case of conflict, the specification of this document, including definitions, will control.

[00013] Each example is provided by way of explanation of the present disclosure and is not a limitation thereon. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to the teachings of the present disclosure without departing from the scope of the disclosure. For instance, features illustrated or described as part of one embodiment can be used with another embodiment to yield a still further embodiment

[00014] While the terms used herein are believed to be well understood by one of ordinary skill in the art, definitions are set forth herein to facilitate explanation of the presently-disclosed subject matter. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the presently-disclosed subject matter belongs. Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the presently-disclosed subject matter, representative methods, devices, and materials are now described. Following long-standing patent law convention, the terms "a", "an", and "the" refer to "one or more" when used in this application, including the claims. Thus, for example, reference to "a cell" includes a plurality of such cells, and so forth. All references to singular characteristics or limitations of the present disclosure shall include the corresponding plural characteristic(s) or limitation(s) and vice versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made.

[00015] All combinations of method or process steps as used herein can be performed in any order, unless otherwise specified or clearly implied to the contrary by the context in which the referenced combination is made. The methods and compositions of the present disclosure, including components thereof, can comprise, consist of, or consist essentially of the essential elements and limitations of the embodiments described herein, as well as any additional or optional components or limitations described herein or otherwise useful.

[00016] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and claims are approximations that can vary depending upon the desired properties sought to be obtained by the presently-disclosed subject matter.

[00017] As used herein, the term "about," when referring to a value or to an amount of mass, weight, time, volume, concentration or percentage is meant to encompass variations of in some embodiments ±20%, in some embodiments ±10%, in some embodiments ±5%, in some embodiments ±1%, in some embodiments ±0.5%, and in some embodiments ±0.1% from the specified amount, as such variations are appropriate to perform the disclosed method.

[00018] As used herein, ranges can be expressed as from "about" one particular value, and/or to "about" another particular value. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about" that particular value in addition to the value itself. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 1 1, 12, 13, and 14 are also disclosed.

[00019] Before explaining the present compositions in detail, it is to be understood that the compositions are not limited to the particular embodiments and that they can be practiced or carried out in various ways.

[00020] The presently disclosed subject matter relates to stabilization of a super-activated peroxy complex with a bridging compound and method for applications in industries such as potable water treatment, cooling water treatment, wastewater treatment, electronic component manufacturing, pharmaceutical manufacturing, pulp and paper industry, food processing, and downhole and downstream applications in the oil and gas industry. The presently disclosed subject matter further relates to a method for preparation of the stabilized super-activated peroxy complexes.

[00021] The bridging compounds stabilize targeted forms of peroxy compound-threatening catalase enzyme including acid-deformed tertiary and quaternary molecular structures by bracing across two sections of that molecule through chemical bonding activity including electrostatic attraction, hydrogen bonding, and covalent bonding.

[00022] Particularly, the presently disclosed subject matter provides a complex that is resistant to rapid breakdown of the super-activated peroxy compounds by catalase enzyme. Catalase enzyme is a natural enzyme produced by the cells of most living plant and animal life. Catalase converts, for example, hydrogen peroxide to non-oxidizing, inactive water and oxygen by serving as a catalyst at rates of up to 500,000 molecules of hydrogen peroxide per molecule of catalase per minute. With the more complex compounds of inorganic and organic peroxides, destruction of free hydrogen peroxide shifts the equilibrium of these molecules back toward their contributing raw material components, releasing more peroxide to be broken down by the undamaged catalase. This rapid destruction occurs for either super- activated or simple peroxy compounds, making practical application of these compounds commercially valueless.

[00023] In industrial applications, peroxy compounds provide oxidation capacity for a wide range of beneficial applications well recognized by those skilled in the art. Super-activation of peroxy compounds has been described in publications (1), whereby strong acids such as sulfuric acid combine with selected peroxy compounds such as hydrogen peroxide to form superacid compounds such as peroxymonosulfuric acid (1), with a range of resonance structures that enhance the strength of subsequent free radicals and create much more active sites for oxidation. The persulfate anion (S₂ 0₈ ^~2 ) from persulfuric acid is the most powerful oxidant of the peroxy compounds (the electromotive force (E) = 2.12 V, as compared to hydrogen peroxide with E = 1.77 V) (FMC, 2001). Unreacted, residual hydrogen peroxide then activates the superacids to form free radicals, resulting in super-activated peroxy compounds.

[00024] With the inherent cost-efficiency of peroxy compounds such as hydrogen peroxide and strong acids such as sulfuric acid, initial review suggests that these super-activated peroxy compounds would be commercially viable and economically valuable. However, as no commercial applications have appeared since the original research in 1898 (1), this proved to not be the case.

[00025] The destructive effect by catalase enzyme in industrial processes, especially produced by ever- present bacteria that assemble catalase as a normal metabolic reaction to the presence of hydrogen peroxide and other peroxy compounds, breaks down added peroxy and super-activated peroxy compounds so rapidly that sufficient addition of fresh peroxy and super-activated peroxy compounds cannot economically occur, and the concentration of peroxide residual maintained drops so low as to make use of pure peroxy and super-activated peroxy compounds inefficient.

[00026] Stewart et. al. in Effect of Catalase on Hydrogen Peroxide Penetration into Pseudomonas aeruginosa Biofilms demonstrated this challenge (4). In Stewart et. al, bacteria aggregates and forms a biofilm, in which the rate of peroxide diffusion was not able to outpace its enzymatic destruction reaction by catalase. In this study, even though hydrogen peroxide was able to diffuse through the biofilm in other examples, biofilms formed from bacteria capable of producing catalase, showed greatly reduced levels of peroxide beneath them, and the remaining peroxide residuals proved incapable of achieving the level of oxidizing reactions to destroy targeted bacteria (4).

[00027] In recognition of this challenge, many attempts have been made to control peroxy compound destruction by catalase. Well-recognized to those skilled in the art are challenges to achieve cost-effective peroxide bleaching of cellulose fibers for the production of paper and paperboard. Especially noted with increased recycle of water intended to lower freshwater demand and to conserve heat energy, catalase is produced by bacteria in the circulating processing waters when exposed to peroxide, and reuse of that water leads to rapid destruction of freshly added peroxide at the front of the process. One attempted option was to raise the processing temperature (5). However, the recommendation to achieve that is to elevate the temperature from the normal level for bleaching of deinked fibers from about 50° C to 70° - 90° C (3), a very substantial increase in required energy with subsequent increases in costs and environmental impact. U.S. Pat. No. 5,885,412 describes a method that uses catalase inhibitors such as hydroxylamine and its associated salts to directly attack the enzyme and its production in bacteria as a reducing agent in an attempt to cost-effectively bleach pulp fibers. However, US20130164814 states that hydroxylamine did not work properly to inhibit catalase. WO2005001056A3 describes a process whereby protease enzyme is used to attack catalase and the bacteria that form it, but there are protease-resistant catalases However, in these attempts, the cost can still be excessive, the efficiency of fiber bleaching less than optimal, and the risk for product and environmental impact greater.

[00028] Other options include combined use with additional biocidal compounds intended to kill the bacteria that produce catalase. U.S. Pat. No. 5,618,385 shows use of halogens including chlorine, bromine, iodine, and chlorine dioxide, and ozone to kill catalase-producing bacteria and break down the catalase they might have formed. U.S. Pat. No. 5,728,263 states that dialdehydes and acetals including glutaraldehyde can help improve bleaching efficiency of peroxide by killing the organisms producing catalase. U.S. Pat. No. 6,432,262 teaches application of hydantoins to accomplish this goal. U.S. Pat. No. 7,214,292 and 7,285, 181 discuss use of phosphines and phosphonium compounds including THP and THPS to kill catalase-producing bacteria. U.S. Pat. No. 7,927,496 teaches use of hypochlorite activated by ammonium compounds to effect a kill. The challenge for all of these is the water-solubility of the catalase enzyme that allows ready distribution throughout the water circuit and the impossibility to kill 100% of bacteria in large industrial systems, especially when water is conserved by its reuse. The presence of even small amounts of peroxide, when contacting catalase-producing organisms, leads to increase of the enzyme levels that will recirculate back into the process, eliminating the peroxy compound levels necessary to achieve the targeted process goals. U.S. Pat. Nos. 5,618,385; 5,728,263; 6,432,262; 7,214,292; 7,285, 181 ; and 7,927,496 are incorporated herein in their entireties by specific reference for all purposes.

[00029] Therefore, peroxy compounds on their own were not economically viable, and alternative oxidizers such as sodium hypochlorite, chlorine gas, chlorine dioxide, hypobromous acids, hydantoins, and ultraviolet light needed to be used to achieve the targeted oxidation required in the industrial processes. These alternatives are less desirable than the peroxy compound options, as they are known to create byproducts that are environmentally hazardous and often carcinogenic. Many halogenated byproducts, including chlorinated and brominated organic compounds and various non-peroxygen free radicals, are identified as hazardous to the environment, including dioxins that are formed from precursors in applications such as pulp mills. Many others have been identified as known or suspect carcinogens, with allowed limitations, for example, of haloacetic acids (HAA) in drinking water to less than 50 ppb (parts per billion).

[00030] In preparation of potable water for drinking and ingestion by humans and pets, typical applications currently use chlorine compounds to oxidize both microbiological and organic contaminants.

[00031] In treatment of cooling water, similar microbiological and organic contaminants are known to cause fouling of surfaces that leads to under-deposit corrosion and extremely costly destruction of concrete and metal assets. Additionally, in cooling water applications such as with ethanol production, byproducts of manufacturing such as distiller's grain are used for animal feed, and no existing alternative biocide can be used due to severe limitations on allowed contaminants.

[00032] In wastewater applications, both microbiological and organic contaminants must be reduced to a regulated concentration prior to release and/or reuse of the treated water, and many of the remaining residuals are known to be hazardous to the flora and fauna that are subsequently exposed. Additionally, residual oxidizers such as from chlorination must be removed by inactivation prior to any discharge to public waters.

[00033] In both electronic component and pharmaceutical manufacturing, residual oxidizing compounds such as chlorine and bromine used to produce the necessary ultra-pure water for processing lead to contamination of the manufactured goods and destructive reduction in their quality by attack from the residual oxidizers.

[00034] In pulp and paper manufacturing, residual oxidizers convert organic compounds either naturally in the raw materials or added for particular effect that are extremely hazardous with environmental release or even in the finished paper and paperboard goods. Also, the high organic loading of process waters makes oxidizers such as chlorine and bromine much less if not completely ineffective.

[00035] In food processing, residual oxidizers can create off odors and tastes, in addition to creating byproducts that can contaminate the food with potentially hazardous chemicals.

[00036] In the oil and gas industry, especially when treating waters that have high contamination with microbiological and organic components, many typical oxidizers are ineffective due to their rapid inactivation by the normally present organic loading. Also, the byproducts of the oxidation reaction are often environmentally hazardous, risking substantial potential liability for leaks and spills. Typical methods to apply stabilized super-activated peroxy compounds could include batch treatment fed down the casing or tubing, with or without flush water, and with or without recirculation; use of coiled tubing and jetting to target treatment by zones; application by higher volume and velocity into the drill pipe; use of a capillary string to treat at the surface or below the subsurface pump; squeeze technology whereby the composition is forced deeper into the formation under pressure; etc. [00037] With the limited value of existing oxidizers and the risks inherent in byproduct formation for the applications in these industries, economic and commercially viable use of peroxy compounds such as hydrogen peroxide and super-activated peroxy compounds would be very valuable. There is a need for new methods for controlling catalase contamination.

[00038] Destructive catalase enzyme is known to be inactivated by molecular deformation of tertiary and quaternary structures at acidic pH. Therefore, preparation of super-activated peroxy compounds, which use strong acids such as sulfuric acid, would seem to reduce the inefficiency caused by catalase with the deformation at the inherently low pH of the super-activated peroxy compounds. However, this low pH deformation is a readily reversible reaction, leading to reactivation of the catalase in microenvironments where there may be a temporary insufficiency of acid available. As the catalase enzyme is so rapid in its destruction of compounds like hydrogen peroxide, even a reduced quantity of active catalase is sufficient to permanently destroy the applied peroxy compounds.

[00039] In some embodiments of the presently disclosed subject matter, certain bridging compounds are discovered to bridge the deformed catalase to stabilize its inactive form. When accomplished, the stabilized deformation of the catalase is highly resistant to the reverse reaction, preventing reformation of the active enzyme with its peroxy compound destructive capacity.

[00040] With a stabilized deformation of catalase enzyme, the full benefit of a super-activated peroxy compound can be realized, as the inactivated enzyme is unable to break down the compound and a cost- effective residual of it can be maintained. With the resulting stabilized solutions of super-activated peroxy compound and elimination of rapid degradation of the oxidizing residual, targeted oxidation becomes cost-effective. Beneficial oxidation can be used in targeted applications including breaking down toxic and corrosive sulfides in processing waters of the oilfield and wastewater, destroying taste and odor contaminants in potable and drinking water, eliminating organic foulants such as paraffins and naphthenics in the oilfield and process contaminants in cooling water, removal of destructive contaminants from processing waters in the electronics and pharmaceutical industries, destruction of fouling biofilm in processing and cooling waters, and elimination of hazardous pollutants in wastewater.

[00041] Preparation of the super-activated peroxy compounds is well known to those skilled in the art, with a blend of at least one strong acid with at least one peroxy compound. In some embodiments, non- limiting examples of the strong acid include hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, or the corresponding partial salts thereof, including but not limited to sodium, potassium, calcium, magnesium, and aluminum. In some embodiments, the peroxy compound includes inorganic peroxides and organic peroxides, hydrogen peroxide, perborates, percarbonates, persulfates, perphosphates, and combinations thereof. [00042] In some embodiments, the super-activated peroxy compound is created by blending of hydrogen peroxide with sulfuric acid, with the ratio of the hydrogen peroxide to the sulfuric acid being from about 1000: 1 to about 1 : 1000. In some embodiments, a ratio is from about 2: 1 to about 1:2. In its subsequent applications, the super-activated compound is used at optimized levels as known to those skilled in the art. In some embodiments, the concentration of the super-activated compound is from about 1 ppm to about 10,000 ppm based upon the peroxy compound addition.

[00043] The addition of the bridging agent(s) can be accomplished in certain embodiments during preparation of the super-activated peroxy compound, prior to its preparation, or subsequent to its preparation. In some embodiments, the bridging compound and the super-activated peroxy compounds are delivered and/or prepared in concentrated form and diluted prior to blending. In other embodiments, the bridging compound may be premixed with the strong acid or the peroxy compound prior to preparation of the super-activated compound. The stabilized super-activated peroxy compound may be prepared on-site at the location for application or off-site in a manufacturing facility prior to shipment and delivery.

[00044] When prepared at the location for use, the stabilized super-activated peroxy compound may be blended in a single vessel prior to transfer to the point of application in its concentrated form or a dilute aqueous solution, or it can be prepared by individual application into a single water line with serial addition of the components in any order prior to the addition at the point of application. When prepared into a single water line, in-line mixers may be used to achieve a more optimal mixing.

[00045] When prepared off-site before delivery to the location, the bridging agent and the super-activated peroxy compound may be combined to form a complete, ready-to-apply formulation of stabilized super- activated peroxy compound in a single vessel by mixture of the bridging agent and the super-activated peroxy compound, or by premixing of the bridging agent with either the strong acid or peroxy compound component prior to formation of the super-activated peroxy compound. To reduce the risk of product degradation such as from exposure to metal ions including iron and manganese, chemical stabilizers known to those skilled in the art to protect peroxy and super-activated peroxy compounds may also be used. This prepared formulation of stabilized super-activated peroxy compound after shipment to its use location can subsequently be added in its concentrated form or in an aqueous dilution.

[00046] For convenience, whether the bridging agent and super-activated peroxy compound are blended at a remote manufacturing location, while in transit to the application site, or immediately prior to addition, the mixing vessel used can be a portable shipping container including pails, drums, IBC (Intermediate Bulk Container) totes, and tanker trucks.

[00047] The bridging compound is combined with the super-activated peroxy compound, with the ratio of bridging compound to the super-activated peroxy compound being from about 1000: 1 to about 1 : 1000, from about 950: 1 to about 1 :950, from 900: 1 to about 1 :900, from about 850: 1 to about 1 : 850, from about 800: 1 to about 1 : 800, from about 750: 1 to about 1 :750, from about 700: 1 to about 1 :700, from about 650: 1 to about 1 :650, from about 600: 1 to about 1 :600, from about 550: 1 to about 1 :550, from about 500: 1 to about 1 :500, from about 450: 1 to about 1 :450, from about 400: 1 to about 1 :400, from about 350: 1 to about 1 :350, from about 300: 1 to about 1 :300, from about 250: 1 to about 1 :250, from about 200: 1 to about 1 :200, from about 150: 1 to about 1 : 150, from about 100: 1 to about 1 : 100, from about 50: 1 to about 1 :50, from about 25 : 1 to about 1 :25, from about 15 : 1 to about 1 : 15, from about 10: 1 to about 1 : 10, from about 5 : 1 to about 1 :5, from about 4: 1 to about 1 :4, from about 3: 1 to about 1 :3, and from about 2: 1 to about 1 :2.

[00048] In some embodiments, the bridging compounds may be organic compounds, their salts, or combinations thereof. In some embodiments, the bridging compound may be an organic acid or blend thereof, including citric, malic, formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, undecanoic, dodecanoic, lactic, maleic, ascorbic, hydroxyacetic, neopentanoic, neoheptanoic, neodecanoic, oxalic, malonic, succinic, glutaric, adipic, pimelic, and subric acid, and salt thereof. Non-limiting examples of the salt of the organic acid is sodium, potassium, calcium, magnesium, and aluminum acid. In some embodiments, the bridging compound selected from among the organic acids has a shorter chain length, such as citric acid, to provide the highest efficiency of stabilization of the deformed catalase.

[00049] In some embodiments, the bridging compound and its resulting dosage to achieve stabilization of a super-activated peroxy compound may be selected to achieve secondary benefits of binding of contaminants for enhanced control or to overcome additional functional demand from potentially interfering ions and compounds. As a non-limiting example, in applications including cleaning of paraffinic and naphthenic deposition downhole in oil and gas wells, calcium ions from the source water and the formation itself, as well as iron ions from both the formation and ongoing corrosion of steel pipe, tubing, and equipment, contribute to fouling, deposition, and scaling of the systems that impact total production and require large investment in cleaning operations and replacement of damaged equipment. Additionally, these contaminants can tie up a substantial portion of the bridging agent that is targeting stabilization of the super-activated peroxy compound by stabilization of deformed catalase. Further, some bridging agents can aggressively corrode construction materials such as steel, and caution in selection of bridging compounds must be maintained. Therefore, an adjustment in selection of the specific bridging compound, as well as a potentially increased dosage, may be necessary to optimize the application to achieve the greatest stabilization of the super-activated peroxy compound with the highest cost-efficiency and lowest damage to surrounding materials of construction. Citric acid, as an example, is known to be a good binding agent for calcium and iron ions, while it causes limited damage to steel and is a relatively poor binding agent for most other metals. In one embodiment for this type application a bridging compound such as citric acid would be selected, however being applied at a dosage elevated to address the specific concentrations of calcium and iron ions at that site that would decrease the amount of residual bridging compound available to inactivate catalase and stabilize the super-activated peroxy compound.

[00050] In some embodiments, the bridging compound may include an organo-carboxylic acid with additional functional groups. In some embodiments, the organo-carboxylic acid includes hydroxyls, additional carboxylic groups, chlorides, sulfates, unsaturation, phosphates, wherein the organo-carboxylic is in undissociated acid form or salts thereof.

[00051] In some embodiments, the bridging compound is available from about 0.1 to about 100% active.

[00052] In some embodiments, the ratio of bridging compound to super-activated peroxy compound may be increased to address functional demand by compounds other than the super-activated peroxy compound, such as with use of hard waters that may have elevated concentrations of calcium and magnesium, or decreased to reduce the residual, excessive, functional capacity of the subsequent solutions.

[00053] In some embodiments of the present disclosure, the bridging compound can be in solid form or liquid form. The bridging compound may be added in a mixing plant on-site or may be incorporated into a formulation with the super-activated peroxy compound and delivered to the application point from an off-site location or other nearby preparation area.

[00054] In some embodiments, the super-activated compound is applied at an optimized rate for it or a similar non-super-activated peroxy compound, as known to those skilled in the art. In those embodiments, the ratio of bridging compound is adjusted to maintain an optimized concentration to meet both the inherent functional demand of the system and to stabilize the deformed catalase enzyme.

[00055] The mixture of the bridging compound and the super-activated peroxy compound can be blended into various formulations with a wide variety of other process additives to increase convenience of the applications and provide process benefit for the combination of the oxidizing capacity of the super- activated peroxy compound with the benefit of the other additives. In some embodiments, these other additives can include acids and acid blends, alkalis and alkali blends, deposit control agents, cleaning formulations and surfactants, thickening agents, foaming agents, defoamers, solvents, scale control agents, corrosion inhibitors, and biocides. In some embodiments, chemical compatibility is verified before the potential blending of the stabilized, super-activated peroxy compound with the other additives.

[00056] Further provided, in some embodiments, the present disclosure provides a method to reuse one or more of the treated water flows to enhance the overall cost-efficacy and further reduce any remaining residual of the stabilized super-activated peroxy compound. In some other embodiments, chemical additives can be applied to decrease or eliminate any remaining undesired residual of super-activated peroxy compound. [00057] EXAMPLES

[00058] Example 1

[00059] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with the bridging compound citric acid in approximately a 2: 1 ratio of super- activated peroxy compound to bridging compound, while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with bridging compound and each control was then used to treat samples of poultry processing wastewater contaminated with high levels of fats, oils, and grease (FOG) at a level targeted to achieve 50 ppm residual hydrogen peroxide. The residual hydrogen peroxide was then determined after 15 minutes contact time.

Average hydrogen peroxide concentration (control) = 2 ppm

Average hydrogen peroxide concentration (treated with bridging compound) = 48 ppm [00060] Example 2

[00061] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with various ratios of the super-activated peroxy compound (SAPC) to the bridging compound citric acid (CA), while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with bridging compound and each control was then used to treat samples of processing water from a beef processing facility contaminated with high concentrations of bacteria and organics at a level targeted to achieve 100 ppm residual hydrogen peroxide. The bacterial levels were then assayed by total aerobic plate counts (TPC) after 15 minutes contact time. Control samples averaged 120,000 cfu (colony forming units).

TPC for (4 SAPC: 1 CA ratio) = 114,000 cfu (5.00% kill)

TPC for (3 SAPC: 1 CA ratio) = 94,000 cfu (21.67% kill)

TPC for (2 SAPC: 1 CA ratio) = 72,000 cfu (40.00% kill)

TPC for (1 SAPC: 1 CA ratio) = 11,300 cfu (90.58% kill)

TPC for (1 SAPC:2 CA ratio) = 830 cfu (99.31% kill)

TPC for (1 SAPC:3 CA ratio) = 1,040 cfu (99.13 % kill)

TPC for (1 SAPC:4 CA ratio) = 1,320 cfu (98.90 % kill)

[00062] Example 3 [00063] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with various bridging compounds in an approximate 2: 1 ratio of super-activated peroxy compound to bridging compound, while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with bridging compound and each control was then used to treat samples of produced water from an operating oil well contaminated with a substantial amount of organics at a level targeted to achieve 50 ppm residual hydrogen peroxide. The residual hydrogen peroxide was then determined after 15 minutes contact time.

Average hydrogen peroxide concentration (control) = None detected

Average hydrogen peroxide concentration (acetic acid) = 21 ppm

Average hydrogen peroxide concentration (citric acid) = 46 ppm

Average hydrogen peroxide concentration (octanoic acid) = 7 ppm

Average hydrogen peroxide concentration (propionic acid) = 18 ppm

Average hydrogen peroxide concentration (succinic acid) = 3 ppm

[00064] Example 4

[00065] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with the bridging compound citric acid (CA) to achieve a 2: 1 ratio with the super- activated peroxy compound, while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with bridging compound and each control was then used to treat samples of municipal wastewater contaminated with soluble sulfides that can release as the corrosive and toxic hydrogen sulfide gas. Treatment levels were targeted to achieve various residual concentrations of hydrogen peroxide. The residual sulfides were then determined after 15 minutes contact time.

60 ppm 24 ppm 60 ppm 2 ppm

80 ppm 24 ppm 80 ppm 1 ppm

100 ppm 18 ppm 100 ppm 1 ppm

[00066] Example 5

[00067] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with the bridging compound citric acid (CA) to achieve a 2: 1 ratio with the super- activated peroxy compound at 4 ppm, while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with the bridging compound and each control was then used to treat samples of river water intended for use as drinking water. After 15 minutes contact time, samples were evaluated for residual bacteria levels and color. Samples were then treated with 0.5 ppm total chlorine by addition of an appropriate quantity of sodium hypochlorite. After 10 minutes, the samples were evaluated for residual chlorine levels.

[00068] Example 6

[00069] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with the bridging compound citric acid (CA) to achieve a 2: 1 ratio with the super- activated peroxy compound at 5 ppm, while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with the bridging compound and each control was then used to treat samples of industrial cooling water from an open recirculating system with a multi-cell cooling tower. This system has frequent contamination from process side leaks. After one hour contact time, samples were evaluated for residual bacteria levels and percent kill.

[00070] Example 7

[00071] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with the bridging compound citric acid (CA) to achieve a 2: 1 ratio with the super- activated peroxy compound at 20 ppm, while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with the bridging compound and each control was then used to treat samples of industrial wastewater from a facility manufacturing steel bearings. Results were compared against the existing disinfection program using sodium hypochlorite at 40 ppm.

[00072] Example 8

[00073] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with the bridging compound citric acid (CA) to achieve a 2: 1 ratio with the super- activated peroxy compound at 10 ppm, while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with the bridging compound and each control was then used to treat samples of process water from the closed loop of a recycle paper machine. Results were compared against the existing disinfection program using sodium hypochlorite at 20 ppm.

[00074] Example 9

[00075] A super-activated peroxy compound was formed by blending the strong acid sulfuric acid with the peroxy compound hydrogen peroxide in a ratio known to those skilled in the art. Aliquots were subsequently treated with the bridging compound citric acid (CA) to achieve a 2: 1 ratio with the super- activated peroxy compound at 50 ppm, while baseline controls were prepared by addition of distilled water to equal the same volume as the treated portions. Each preparation treated with the bridging compound and each control was then used to treat samples of frac water intended for use in a fracturing process downhole. Results were compared against the existing disinfection program using sodium hypochlorite at 100 ppm.

EXA M PL E Oi l I I I I I) I RA( WATE R K i l l . STl

Sample Bacteria (TPC) % Kill Control A 620,000 cfu -

Control B 930,000 cfu -

Average 775,000 cfu -

Sodium hypochlorite 103,000 86.71%

Sample A 62,000 cfu 92.00%

Sample B 45,000 cfu 94.19%

Sample C 38,000 cfu 95.10%

[00076] All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference, including the references set forth in the following list:

REFERENCES

1. Caro, H. ZurKenntniss der Oxydationaromatischer Amine. Zeitschriftfiirangewandte Chemie. Vol. 36. Pp 845-846.

2. FMC Corporation. Persulfates - Technical Information (company brochure). 2001.

3. Kopania, Ewa; Stupinska, Halina; and Palenik, Jaroslaw. Susceptibility of Deinked Waste Paper Mass to Peroxide Bleaching. Fibres& Textiles in Eastern Europe. Vol. 16, No. 4 (69). 2008. Pp 1 12 - 1 16.

4. Stewart, Philip; Roe, Frank; Rayner, Joanna; Elkins, James G.; Lewandowski, Zbigniew; OchsnerUrs A.; and Hassett, Daniel J. Effect of Catalase on Hydrogen Peroxide Penetration into

Pseudomonas aeruginosa Bio films. Applied and Environmental Microbiology. February, 2000. Pp 836- 838.

5. Worrell, Ernst; and Reuter, Markus A. Handbook of Recycling. Elsevier, Waltham, MA. 2014.

Claims

What is claimed is:

I . A composition, comprising one or more super-activated peroxy compounds with one or more stabilizing bridging compounds.

2. The composition of claim 1, wherein the super-activated peroxy compound comprises a blend of one or more strong acids comprising hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid, or the corresponding partial salts thereof, including sodium, potassium, calcium, magnesium, and aluminum, and one or more peroxy compounds selected from a group comprising inorganic peroxides and organic peroxides, hydrogen peroxide, perborates, percarbonates, persulfates, perphosphates, and combinations thereof.

3. The composition of claim 1, wherein the one or more bridging compound comprises an organic acid or blend thereof.

4. The composition of claim 3, wherein the organic acid is non-polar in acid conditions.

5. The composition in claim 4, wherein the organic acid is polyprotic

6. The composition in claim 3, wherein the organic acid comprises citric, malic, formic, acetic, propionic, butanoic, pentanoic, hexanoic, heptanoic, octanoic, nonanoic, decanoic, undecanoic, dodecanoic, lactic, maleic, ascorbic, hydroxyacetic, neopentanoic, neoheptanoic, neodecanoic, oxalic, malonic, succinic, glutaric, adipic, pimelic, and subric acid, and salts thereof.

7. The composition of claim 3, wherein the salt of the organic acid comprises sodium, potassium, calcium, magnesium, and aluminum, and phosphoric acid.

8. The composition of claim 1, wherein the one or more bridging compound comprises an organo-carboxylic acid with additional functional groups comprising hydroxyls, additional carboxylic groups, chlorides, sulfates, unsaturation, phosphates, wherein the organo-carboxylic is in undissociated acid form or salts thereof.

9. The composition of claim 1, wherein the one or more bridging compound is a citric acid.

10. The composition of claim 9, wherein the citric acid provides the optimal structural bridge to stabilize the deformed catalase.

I I . The composition of claim 9, wherein citric acid provides additional functional activity to enhance control of contaminants comprising calcium, magnesium, and iron salts.

12. The composition of claim 1, wherein the bridging compound stabilizes deformed catalase enzyme by bridging of the deformed structure.

13. The composition of claim 12, wherein the stabilization of the deformed catalase provides stabilization of a super-activated peroxy compound by limiting its destruction through enzymatic breakdown by active catalase.

14. The composition of claim 1, wherein the one or more bridging compounds is in liquid or solid form.

15. The composition of claim 1, wherein the one or more bridging compound is about 0.1% to about 100% percent active.

16. The composition of claim 1, wherein the one or more bridging compound is added before, during, or after preparation of the super-activated peroxy compound.

17. The composition of claim 1, wherein the blend of bridging compound and super-activated peroxy compound is prepared on-site, at the point of application, in-line prior to the application, or off- site at a manufacturing location.

18. The composition of claim 1, wherein the blend of bridging compound and super-activated peroxy compound is prepared into a formulation, wherein the formulation is a stabilized super-activated peroxy compound.

19. The composition of claim 18, wherein the formulation further comprises other functional additives comprising product stabilizers, acids and acid blends, alkalis and alkali blends, deposit control agents, cleaning formulations and surfactants, thickening agents, foaming agents, defoamers, solvents, scale control agents, corrosion inhibitors, and biocides.

20. The composition of claim 1, wherein the composition can be applied in combination with other functional additives comprising acids and acid blends, alkalis and alkali blends, deposit control agents, cleaning formulations and surfactants, thickening agents, foaming agents, defoamers, solvents, scale control agents, corrosion inhibitors, and biocides.

21. The composition of claim 1, wherein the ratio of bridging compound to super-activated peroxy compound is 1 : 1000 to 1000: 1.

22. The composition of claim 1, wherein the ratio of bridging compound to super-activated peroxy compound is adjusted for additional functional demand from the baseline conditions of the system prior to addition of the bridging compound and super-activated peroxy compound.

23. The composition of claim 1, wherein the bridging compound is blended with the super- activated peroxy compound in a shipping container by separate addition or simultaneous addition.

24. A composition of claim 1, wherein the stabilized super-activated peroxy compound is used in an industrial processes to cost-effectively produce a targeted oxidizing reaction, wherein the industrial process comprises breaking down toxic and corrosive sulfides in processing waters of the oilfield and wastewater, destroying taste and odor contaminants in potable and drinking water, eliminating organic foulants such as paraffins and naphthenics in the oilfield and process contaminants in cooling water, removal of destructive contaminants from processing waters in the electronics and pharmaceutical industries, destruction of fouling biofilm in processing and cooling waters, or elimination of hazardous pollutants in wastewater.

25. A method of stabilizing the super-activated peroxy compound, comprising, preparing one or more super-activated peroxy compounds by mixing at least one strong acid with at least one peroxy compound, and adding one or more bridging compounds.

26. The method of claims 25, wherein the one or more bridging compounds is added before, during, or after preparation of the super-activated peroxy compound.

27. The method of claim 25, wherein the blend of bridging compound and super-activated peroxy compound is prepared on-site, at the point of application, in-line prior to the application, or off- site at a manufacturing location.

28. The method of claim 25, further comprising adding at least one functional additive comprising product stabilizers, acids and acid blends, alkalis and alkali blends, deposit control agents, cleaning formulations and surfactants, thickening agents, foaming agents, defoamers, solvents, scale control agents, corrosion inhibitors, or biocides.

29. The method of claim 25, wherein the ratio of bridging compound to super-activated peroxy compound is 1 : 1000 to 1000: 1.

30. The method of claims 25, wherein the bridging compound is added with the super- activated peroxy compound in a shipping container by separate addition or simultaneous addition.

31. A method of treating water flows, comprising adding the composition of claim 1 to water flows.

32. The method of claim 31, wherein the water flows can be reused.

33. A method of claim 31, wherein the water flow treated with stabilized super-activated peroxy compound is used in an industrial processes to cost-effectively produce a targeted oxidizing reaction, wherein the industrial process comprises breaking down toxic and corrosive sulfides in processing waters of the oilfield and wastewater, destroying taste and odor contaminants in potable and drinking water, eliminating organic foulants such as paraffins and naphthenics in the oilfield and process contaminants in cooling water, removal of destructive contaminants from processing waters in the electronics and pharmaceutical industries, destruction of fouling biofilm in processing and cooling waters, or elimination of hazardous pollutants in wastewater.