• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The claimed invention relates to a process for mechanically modifying strong acid/salt solutions and strong base/salt solutions, where the modifications result in a stable solution that has effective reactivity with covalent bonds while exhibiting non- corrosive and dermal-friendly properties.
    公开号:AU2013208049A1
    申请号:U2013208049
    申请日:2013-01-09
    公开日:2014-08-14
    发明作者:Burt R. Sookram；John W. Veenstra
    申请人:NBIP LLC；
    IPC主号:C01B11-00
    专利说明:
    WO 2013/106455 PCT/US2013/020864 1 Reactive, Non-Corrosive and Dermal-Friendly Compositions and Methods CROSS-REFERENCES TO RELATED APPLICATIONS [0001] This Application is a continuation-in-part of U.S. Patent 5 Application Ser. No. 13/346,160, filed January 9, 2012, which is incorporated herein by reference in its entirety as if fully set forth herein. FIELD OF THE INVENTION [0002] The claimed invention is directed to strong-acid/salt and strong 10 base/salt compositions that have been mechanically modified to be highly reactive yet stable, non-corrosive and dermal-friendly. BACKGROUND OF THE INVENTION [0003] Hydrochloric acid (HCl), a polar molecule, dissolves in water
    (H
    2 0), another polar molecule, by shifting a positive hydrogen nucleus 15 (proton) away from the acid to the water, leaving a hydronium cation
    (H
    3 0*) and a chlorine anion (Cl). This is commonly represented by the equation "H 2 0 + HCl -- H 3 0* + Cl- where the" -" indicates that the dissociation of the acid is almost entirely one-way, a characteristic of a "strong acid." Similarly, sodium hydroxide (NaOH), a base, dissolves in 20 water to form a sodium cation (Na*) and a hydroxide anion (OH-). This is commonly represented by the equation "NaOH--Na* (aq) + OH- (aq)" (or alternatively, "NaOH + (H 2 0), [0004] [Na(H 2 0),]* + OH-"), where the "- " indicates that the dissociation of the base is almost entirely one-way, a characteristic of a 25 "strong base." [0005] As a practical matter, any given atom or molecule is "reactive" with another if, under the right set of circumstances, it will interact with the WO 2013/106455 PCT/US2013/020864 2 other molecule by breaking existing bonds and/or forming new bonds. Because strong acids and bases disassociate in water to their ionic components almost completely in water, they are highly reactive with other molecules. For example, because of their polar nature, H30+ and 5 OH- may affect weaker intermolecular bonds, they may break some covalent bonds, and they may form new bonds and new molecules. [0006] Strong acids and bases, however, have other properties which make them unsuitable for use in dermal environments such as medical and cosmeceutical applications. For example, with hydrochloric acid, the 10 disassociated chlorine anion reacts with metal, corroding and weakening the metal and releasing hydrogen gas. This property makes storage of hydrochloric acid in metal containers both problematic and potentially dangerous. Further, although the outermost layer of the epidermis (skin) includes a layer of dead cells that protect the living cells beneath, if the 15 hydrochloric acid is sufficiently concentrated, it can destroy that layer of dead skin cells, exposing the more vulnerable dermal cells beneath. This property renders concentrated hydrochloric acid generally unsuitable for use in applications where it will come into contact with skin. Likewise, a strong base, such as sodium hydroxide, may etch glass containers and 20 can destroy and/ or burn skin cells, and thus, like hydrochloric acid, is problematic to use and store. [0007] The reactive nature of a strong acid or base can be controlled by diluting it in sufficient water; however, the volume of the diluted acid or base needed to provide sufficient H 3 0+ or OH- makes this tactic 25 impractical. Alternatively, the strong acid or base may be combined with an appropriate salt. For example, if water, hydrochloric acid, and ammonium chloride are combined in solution, the intermolecular interactions between the H 3 0+, NH 4 +, and Cl-are sufficient to keep the solution from corroding metals and from irritating or destroying skin. 30 Likewise, if water, sodium hydroxide, and ammonium hydroxide are combined in solution, the intermolecular interactions between the Na+, WO 2013/106455 PCT/US2013/020864 3 NH4+, NH2-, and OH-are sufficient to keep the solution from irritating or destroying skin. However, these same intermolecular interactions leave the solution insufficiently reactive to affect covalent bonds. [0008] What is needed, therefore, is a composition that is reactive like a 5 strong acid or strong base, yet can be safely stored and used in dermal environments, such as in medical and cosmeceutical applications. SUMMARY OF THE INVENTION [0009] An embodiment of the invention is directed toward using a pulsed direct current to energize a solution of a concentrated strong acid or base, 10 a salt, and water, such that the resulting composition does not have the expected corrosive or caustic properties and does not have the expected skin-damaging properties, yet it is sufficiently reactive to affect covalent bonds. A further embodiment of the invention is directed at the resulting composition. 15 BRIEF DESCRIPTION OF THE DRAWINGS [00010] FIG. 1 is a flowchart of a preferred embodiment of the inventive process using a strong acid; [00011] FIG. 2 is a flowchart of an alternative embodiment of the inventive process using a strong acid; 20 [00012] FIG. 3 is a block diagram of preferred equipment used in performing an embodiment of the inventive process; [00013] FIG. 4 is a block diagram of alternative equipment used in performing an embodiment the inventive process; [00014] FIG. 5 is a flowchart of a preferred embodiment of the inventive 25 process using a strong base; and [00015] FIG. 6 is a flowchart of an alternative embodiment of the WO 2013/106455 PCT/US2013/020864 4 inventive process using a strong base. DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS [00016] In this specification and in the claims that follow, reference will be made to a number of terms that shall be defined to have the following 5 meanings: [00017] Throughout this specification, unless the context requires otherwise, the word "comprise," or variations such as "comprises" or "comprising," will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of 10 integers or steps. [00018] It must be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a carrier" includes mixtures of two or more such carriers, and the like. 15 [00019] Ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations by use of the antecedent "about," it will be understood that the particular value 20 forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and independently of the other endpoint. [00020] "Admixture" or "blend" as generally used herein means a physical combination of two or more different components 25 [00021] "Biocide" is used herein to refer to compositions that are biologically active against microbiological contaminates. [00022] "Covalent Bonds" as used herein means the forces that hold atoms together that share electrons and are referred to as strong bonds.
    WO 2013/106455 PCT/US2013/020864 5 [00023] "Dermal Environment" as used herein refers to the multiple layers of skin tissue associated with either humans or animals. [00024] "Intermolecular Attractions" as used herein refers to the attractions between one molecule and a neighboring molecule. 5 [00025] "Microbiological" as used herein refers to any inclusion or growth of harmful microorganisms such as mold, mildew, viral or bacterial contamination. [00026] "Microbiological Count" as used herein refers to the amount or number of microbiological contaminates present on any surface. 10 [00027] "Optional" or "optionally" means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not. [00028] "Pathogen" is used herein to refer to mold, mildew, bacteria, viruses or 15 other microorganisms that can cause contamination on a surface. [00029] "pH" as used herein as a number that is measured in a 1% solution of the strong acid or strong base with the remainder of the solution being water. [00030] "1% solution" is used herein is defined as 1 part of the strong acid or strong base or an acid/salt mixture or base/salt mixture and 99 parts of water. 20 [00031] "Pulse or pulsing" as used herein refers to as a single application of a direct current to a solution. Multiple pulsing or pulses make up a pulsing event. [00032] "Pulsing Event" as used herein refers to a series of pulses followed by a resting period. There can be multiple pulsing events in a single iteration of 25 the inventive method.
    WO 2013/106455 PCT/US2013/020864 6 [00033] "Strong Acids" is used herein to refer to any acid with a pH of 0.1 to 3.5 for a 100% solution of the acid. [00034] "Strong Bases" is used herein to refer to any base with a pH of 10.1 to 14.0 for a 100% solution of the base 5 [00035] "Strong Acid/Salt" when referring to the salt combined with an acid is used herein to refer to any salt that will effectively combine with the chosen acid. [00036] "Strong Base/Salt" when referring to the salt combined with a base is used herein to refer to any salt that will effectively combine with the chosen 10 base. [00037] By "sufficient amount" and "sufficient time" means, an amount and time needed to achieve the desired result or results, e.g., control and/or prevention of microbiological contamination. [00038] A "weight percent" of a component, unless specifically stated to the 15 contrary, is based on the total weight of the formulation or composition in which the component is included. Strong acid embodiments [00039] FIG. 1 shows a flowchart of a preferred embodiment of the inventive process using a strong acid, namely hydrochloric acid. In step 20 1A, 1000 grams of 50% concentrated hydrochloric acid is placed into a 2000 ml glass beaker 101. In step 1B, about 169 grams of crystalline 99% pure ammonium chloride i s a d d e d to beaker 101. The addition of the ammonium chloride generates heat, t h e amount of which depends on the rate at which we added 25 the ammonium chloride into the mixture. T he mixture w a s s t i r r e d r e g u 1 a r 1 y. In step 1C, once all of the ammonium chloride is dissolved in the acid, the solution i s a ll o w e d t o cool to about 650 C. At this point, the solution contains a mix of hydronium and ammonium cations, WO 2013/106455 PCT/US2013/020864 7 and hydroxide and chlorine anions; the measured conductivity was less than 100 mV, the measured proton count was about 1.0 x 10 per pb (where p b is a measure of proton count), and the pH was about 1.3 to 1.4. Where numeric values or ranges of values of conductivity, proton 5 count, or pH of the solution are disclosed or claimed, it refers to conductivity measurements made on the 100 % pure solution, proton count measurements made on a 1.0% solution, and pH measurements made on a 1.0% solution. [00040] Based on empirical observations, at this stage of the process, the 10 attractions between the oppositely charged ions in the solution make it less corrosive and more dermal-friendly than hydrochloric acid. However, the solution lacks those qualities that would make it sufficiently reactive to disrupt covalent bonds. [00041] In step ID, two electrodes 102 and 103 are placed into the beaker 15 101 at opposite sides of the beaker, away from the walls of the beaker, and partially submerged in the solution. The electrodes 102 and 103 are connected to a direct current power source 104 with an inline switch 105. Switch 105 could be a manual switch, but in practice, a strobe light controller, laboratory voltage pulser, or comparable circuit c a n b e u s e d 20 to provide the direct current pulses. Fig. 3 shows a block diagram of the equipment used in a preferred embodiment of the inventive process. [00042] In step 1E, a 3 amp direct current at 10 volts is pulsed through the solution between the electrodes for about 30 minutes, where the pulsing period was about 20 seconds on and 20 seconds off. After allowing the 25 solution to cool in Step iF, the measured conductivity was found to be 25 about 495 mV; the measured proton count was about 0.95 x 10 and the pH was about 1.21. [00043] In Step 1G, after the first period of pulsing the current through the solution and after the solution had cooled, a second round of pulsing was 30 performed, comparable to the first and lasting a length of about 30 WO 2013/106455 PCT/US2013/020864 8 minutes. After this second round of pulsing, the measured conductivity was about 1120 mV; the measured proton count was about 0.95 x 1025 and the pH was about 1.20. Over time (several months) the conductivity did not measurably decrease, suggesting that the second round of pulsing 5 not only increased the reactivity, but a ls o added stability to the composition. [00044] While not being bound to specific theories, based on empirical observations, the controlled application of direct current increases the lengths of the bonds in the polar molecules, leading to higher reactivity. 10 Further, because the current is pulsed, it does not interfere with the intermolecular bonds between the oppositely-charged ions (and in fact strengthens those bonds), thus retaining and enhancing the composition's non-corrosive and dermal-friendly qualities. Further, because of the stability of the intermolecular bonds, when the composition is stored 15 under non-adverse conditions (for example, away from extreme heat, light, pressure, or electromagnetic radiation), it retains its reactive, non corrosive, and dermal-friendly qualities indefinitely. Further, when steady (non-pulsed) or alternating current, or higher-power current is used, or when the temperature is not controlled during the pulsing process, the 20 composition did not have these enhanced reactive, non-corrosive, and dermal-friendly qualities. This does not, however, preclude the use of other energy sources, such as sound, electricity, light, or mechanical sources, provided the application of energy does not break down the intermolecular bonding. Thus, this embodiment addresses the need for a 25 stable composition that is reactive, like a strong acid, yet does not corrode metal or irritate skin. [00045] In other embodiments, the concentration of the acid may be varied without affecting the general process or the characteristics of the resulting composition; however, use of too weak of a concentration may lower the 30 ranges of conductivity and proton count in the final composition and therefore limit its usefulness.
    WO 2013/106455 PCT/US2013/020864 9 [00046] In the embodiment described above, pulsing of the solution occurred in two steps. This was to help control the temperature of the solution, as it was found that excessive heat appeared to break down intermolecular bonds instead of simply energizing them, leading to a 5 solution that did not have the desired properties. In other embodiments, the pulsing can occur in a single step, provided that the temperature of the solution is kept under about 90'C using cooling techniques that are known in the art, for example, partially submersing the mixing vessel in a cooling bath, as shown in the block diagram of FIG. 4. The process described in 10 the flowchart of FIG. 2 differs from the process of FIG. 1 in that after the HCl and NH 4 Cl are mixed together, the beaker 101 is placed into a cooling bath 106, which maintains the temperature during charging, and the pulsing process is performed in a single 60-minute step. [00047] In other embodiments, the voltage, amperage, period, and 15 duration of the pulsing current could be varied without adversely affecting the desired properties. Such variations could be necessitated, for example, by the size of the electrodes, the size of the beaker, and the volume of the acid/salt solution. In practice, the desired properties of the modified acid/salt solution c a n b e a c h i e v e d with voltages ranging from 4 to 20 16 volts, currents ranging from 1 to 20 amps, pulse periods ranging from 5 to 60 seconds on and 5 to 60 seconds off, and pulsing current duration ranging from 20 to 70 minutes. In determining these ranges, we applied the pulsing current at 1 atmosphere; varying the pressure could broaden or narrow these ranges without affecting the end results, and new 25 effective ranges for different pressure constraints could be determined through routine experimentation. [00048] In a preferred embodiment, we used quantities of the various components commensurate with what was practical in a laboratory setting; obviously, in an industrial production setting, the quantities of the 30 various components used would be a function of the manufacturing equipment and desired amount of final product. Designing the optimal WO 2013/106455 PCT/US2013/020864 10 manufacturing environment can be derived from the embodiments disclosed in this patent using routine chemical engineering techniques. [00049] In other embodiments, the ammonium chloride salt can be replaced with other chloride salts such as, for example, sodium chloride, 5 potassium chloride, calcium chloride, magnesium chloride, aluminum chloride, zinc chloride, nickel chloride, lead chloride, copper chloride, ferrous chloride, ferric chloride, gold chloride, or comparable chloride salts (or combinations of chloride salts). Alternatively, the inventive composition can use a chlorite salt, for example, sodium chlorite, 10 potassium chlorite, calcium chlorite, ammonium chlorite, magnesium chlorite, aluminum chlorite, or comparable chlorite salts (or combinations of such chlorite salts). The choice of one particular salt over another does not affect the general process or characteristics of the resulting composition; however, the choice of a particular salt and its 15 purity may change the proportions of the various components used in the process, it may change the measured ranges of conductivity and proton count of the composition, and selection of a particular salt may result in the composition having useful or detrimental characteristics beyond those described here. The optimal quantities of components and 20 length/magnitude of current pulsing for any given substitute salt can be determined from routine experimentation based on the embodiments disclosed in this patent. [00050] In other embodiments, the hydrochloric acid can be replaced with another strong acid. By way of example, the following strong acids could 25 be used: hydroiodic acid (HI), hydrobromic acid (HBr), sulfuric acid
    (H
    2
    SO
    4 ), nitric acid (HNO3), and chloric acid (HClO 3 ). The choice of one particular acid over another does not affect the general process or characteristics of the resulting composition; however, the choice of a particular acid and its purity may change the proportions of the various 30 components used in the process, it may change the measured ranges of conductivity and proton count of the composition, and selection of a WO 2013/106455 PCT/US2013/020864 11 particular acid may result in the composition having useful or detrimental characteristics beyond those described here. The optimal quantities of components and length/magnitude of current pulsing for any given substitute acid can be determined from routine experimentation based on 5 the embodiments disclosed in this patent. [00051] In selecting substitute acid and/or salt components, we have found the following guidelines to be true. First, we found that ammonium salts were preferable over non-ammonium salts. While not binding ourselves to specific theories, we believe that because of its size and polarity, the NH 4 ' 10 tends to form relatively stable intermolecular bonds with negatively charged anions (for example, Cl-), even after the direct current pulsing step. Thus the composition remains non-corrosive and dermal- friendly after charging, but the increased polarity makes the composition sufficiently reactive to disrupt other intermolecular bonds. This preference 15 for an ammonium salt notwithstanding, non- ammonium salts which disassociate into cations that behave similarly to NH 4 ' may prove suitable, especially in applications where a non-ammonium salt brings additional benefits. [00052] Second, we found selecting a salt with the same or similar anion to 20 the acid (for example, Cl-) was preferable over those with dissimilar anions. We believe that with a more homogenous the solution, there will be fewer undesirable side reactions. However, selecting an acid and salt with dissimilar anions may nonetheless prove suitable, especially in applications where the dissimilar anion of the salt brings additional 25 benefits. [00053] Thus, using these guidelines, by way of example and not limitation, the following acid and salt pairs could be used: hydroiodic acid (HI) and ammonium iodide (NH 4 I), hydrobromic acid (HBr) and ammonium bromide (NH4Br), sulfuric acid (H2SO 4 ) and ammonium 30 sulfate (NH4SO4), nitric acid (HNO3) and ammonium nitrate (NH4NO3), WO 2013/106455 PCT/US2013/020864 12 and chloric acid (HC103) and ammonium chlorate (NH4C103). We note, however, that because some of these acid/salt combinations can be highly reactive (ammonium nitrate, for example, is used as an oxidizing agent in explosives, and ammonium perchlorate is used as a solid rocket 5 propellant); the steps required to maintain safe production may make those combinations economically impractical. [00054] Finally, while we specifically note the use of the modified s t r o n g acid/salt compositions in the context of affecting covalent bonds, our inventive composition is not limited to such anti 10 microbiological uses. Indeed, we believe that our inventive composition may prove useful in any application where a reactive acid-based composition is needed, but where the composition must be non-corrosive and dermal-friendly. For example, we believe that the composition would be useful in hydraulic fracturing, applications 15 requiring the use of an electrolyte, removal of carbonates and silicates, PCB removal and cleanup, and soil remediation following the over-use of urea. Strong base embodiments [00055] FIG. 5 shows a flowchart of a preferred embodiment of the 20 inventive process using a strong base, namely sodium hydroxide (NaOH). In step 5A, 1000 grams of a 50% pure sodium hydroxide in the form of solid beads was placed into a 2000 ml glass beaker 101. In step 5 B, about 239 grams of ammonium hydroxide with a maximum of 44% ammonia was added to the beaker. The addition of 25 the ammonium hydroxide generates heat, t h e a m o u n t o f w h i c h d e p e n d s o n t h e rate at which we added the ammonium hydroxide into the mixture. The mixture was stirred regularly. In step 5C, once all of the ammonium hydroxide was dissolved in the sodium hydroxide, the solution w a s a 11 o w e d to cool to about 65 0 C. At this 30 point, the solution contained a mix ofNa+, NH 4 +, NH 2 -, and OH-, the WO 2013/106455 PCT/US2013/020864 13 measured conductivity of the solution was less than 100 mV, the measured proton count was about 3.1 x 102 and the pH was about 12.1 for a 1.0 % w/w solution. [00056] At this stage of the process, the attractions between the oppositely 5 charged ions in the solution made it less caustic and more dermal friendly than sodium hydroxide. However, the solution lacked those qualities that would make it sufficiently reactive to disrupt covalent and intermolecular bonds. [00057] In step 5D, two electrodes 102 and 103 were placedinto the 10 beaker 101 at opposite sides of the beaker, away from the walls of the beaker, and partially submerged in the solution. The electrodes 102 and 103 were connected to a direct current power source 104 with an inline switch 105, allowing the current to turn on and off. Switch 105 could be a manual switch, but in practice, we found that we could use a 15 strobe light controller, laboratory voltage pulser, or comparable circuit to provide the direct current pulses. FIG. 3 shows a block diagram of the preferred equipment used in an embodiment of the inventive process. [00058] In step 5E, we pulsed a 3 amp direct current at 10 volts through the solution between the electrodes for about 30 minutes, where the 20 pulsing period was about 20 seconds on and 20 seconds off. After allowing the solution to cool in Step 5F, we found the measured conductivity was about 85 mV, the measured proton count was about 24 3.1 x 10 , and the pH of a 1% solution w / w was about 12.21. [00059] In step 5G, after the first period of pulsing the current through 25 the solution, and after the solution had cooled for about four hours, we performed a second round of pulsing, comparable to the first and lasting a length of about 30 minutes. After this second round of pulsing, the measured conductivity was about 87 mV, the measured proton count 26 was about 2.8 x 10 and the pH was about 12.20. Over time 30 (several months) the conductivity did not measurably decrease, WO 2013/106455 PCT/US2013/020864 14 suggesting that the second round of pulsing not only increased the reactivity but added stability to the composition. [00060] While not being bound to specific theories, based on our empirical observations, we believe that the controlled application of direct current 5 increases the lengths of the bonds in the polar molecules, leading to higher reactivity. Because the current is pulsed, it does not interfere with the intermolecular bonds between the oppositely-charged ions, thus retaining the composition's non-caustic and dermal- friendly qualities. Further, because of the stability of the intermolecular bonds, when the composition 10 is stored under non-adverse conditions (for example, away from heat, light, pressure, or electromagnetic radiation), it retains its reactive, non caustic, and dermal- friendly qualities indefinitely. Further, consistent with our observations, we found that when we used steady (non-pulsed) or alternating current, or higher-power current, or when we failed to control 15 the temperature during the pulsing process, the composition did not have these enhanced reactive, non-caustic, and dermal-friendly qualities. (This does not, however, preclude the use of other energy sources, such as sound, electricity, light, or mechanical sources, provided the application of energy does not break down the intermolecular bonding.) Thus, this 20 embodiment addresses the need for a stable composition that is reactive, like a strong base, yet does not corrode metal or glass or irritate skin. [00061] In other embodiments, the concentration of the base may be varied without affecting the general process or the characteristics of the resulting composition; however, use of too weak of a concentration may 25 lower the ranges of conductivity and proton count in the final composition and therefore limit its usefulness. The efficacy of a given concentration of base can be determined from routine experimentation based on the embodiments disclosed in the instant application. [00062] In an embodiment described above, pulsing of the solution 30 occurred in two steps. This was to help control the temperature of the WO 2013/106455 PCT/US2013/020864 15 solution, as we found that temperatures above 120'C appeared to break down intermolecular bonds instead of simply energizing them, leading to a solution that did not have the desired properties. In other embodiments, the pulsing can occur in a single step, provided that the 5 temperature of the solution is kept under about 65 C using cooling techniques that are known in the art, for example, partially submersing the mixing vessel in a cooling bath, as shown in the block diagram of FIG. 4. The process described in the flowchart of FIG. 6 differs from the process of FIG. 5 in that after the NaOH and NH 40H are mixed 10 together, the beaker 101 is placed into an cooling bath 106, which maintains the temperature during charging, and the pulsing process is performed in a single 60-minute step. [00063] In other embodiments, the voltage, amperage, period, and duration of the pulsing current could be varied without adversely affecting the 15 desired properties. Such variations could be necessitated, for example, by the size of the electrodes, the size of the beaker, and the volume of the base/salt solution. In practice, we found that we could obtain the desired properties of the modified strong base/salt solution with voltages ranging from 4 to 16 volts, currents ranging from 2 to 5 amps, 20 pulse periods ranging from 5 to 60 seconds on and 5 to 60 seconds off, and pulsing current duration ranging from 20 to 60 minutes. In determining these ranges, we applied the pulsing current at 1 atmosphere; varying the pressure could broaden or narrow these ranges without effecting the end results, and new effective ranges for different 25 pressure constraints could be determined through routine experimentation. Working Examples [00064] A 1% solution using the Potassium based product was evaluated using AOAC Official Method 961.02 (Germicidal Spray Products as Disinfectants) 30 and from ASTM E21 11-00 (Standard Quantative Carrier Test Method to WO 2013/106455 PCT/US2013/020864 16 Evaluate Bactericidal, Fungicidal, Mycobactericidal, and Sporicidal; Potencies of Liquid Chemical Germicides). [00065] Three inoculated slides and an uninoculated control slide were sprayed for 10 seconds from a distance of 10 inches with the test product. The slides 5 were evenly saturated and incubated, then excess fluid drained away. [00066] The results in Table 1 show the tabulated results. Table 1 Average # of recovered colonies (cfu/ml)* Treatment Salmonella Typhimuriun Escherichia coli Average Percent 1OReduction Untreated Control 1.6 X10 5 4.0 X 10 5 Not Applicable Slide 1 < 1.0 ** < 1.0 * > 99.999% (>5 log 10 Reduction) 15 Slide 2 < 1.0 < 1.0 > 99.999% (>5 log 10 Reduction) Slide 3 < 1.0 < 1.0 > 99.999% 20 (>5 log 10 Reduction) * The number of viable microbiological colonies was determined by spreading the plating onto TSA agar plates. Plates were incubated at 36.5 deg C for 24-48 hours. ** No microbiological colonies were observed on any of the plates. None detected when 1.0 25ml inoculum was assayed. [00067] In a preferred embodiment, we used quantities of the various components commensurate with what was practical in a laboratory setting; in an industrial production setting, the quantities of the various components used would be a function of the manufacturing equipment 30 and desired amount of final product. Designing the optimal manufacturing environment can be derived from the embodiments disclosed in this application using routine chemical engineering WO 2013/106455 PCT/US2013/020864 17 techniques. [00068] The choice of one particular salt over another does not affect the general process or the characteristics of the resulting composition; however, the choice of a particular salt and its purity may change the 5 proportions of the various components used in the process, it may change the measured ranges of conductivity and proton count of the composition, and a given salt may result in the composition having useful characteristics beyond those described here. The optimal quantities of components and length/magnitude of current pulsing for any given 10 substitute salt can be determined from routine experimentation based on the embodiments disclosed in this patent. [00069] In other embodiments, the sodium hydroxide can be replaced by another strong base. By way of example, the following strong bases could be used: lithium hydroxide (LiOH), potassium hydroxide (KOH), 15 rubidium hydroxide (RbOH), cesium hydroxide (CsOH), calcium hydroxide (Ca(OH) 2 ), strontium hydroxide (Sr(OH) 2 ), barium hydroxide (Ba(OH) 2 ), and magnesium hydroxide (Mg(OH) 2 ). The choice of one particular base over another does not affect the general process or characteristics of the resulting composition; however, the choice of a 20 particular base and its purity may change the proportions of the various components used in the process, it may change the measured ranges of conductivity and proton count of the composition, and selection of a given base may result in the composition having useful or detrimental characteristics beyond those described here. The optimal quantities of 25 components and length/magnitude of current pulsing for any given substitute base can be determined from routine experimentation based on the embodiments disclosed in this patent [00070] In selecting substitute base and/or salt components, we have found the following guidelines to be true. First, we found that ammonium 30 hydroxide salt was preferable over non-ammonium hydroxide salts. While WO 2013/106455 PCT/US2013/020864 18 not binding ourselves to specific theories, we believe that because of its size and polarity, in the presence of a strong base, the ammonium hydroxide will act like a weak acid, in that it will lose a proton, yielding an amide anion (NH2-), which tends to form relatively stable intermolecular 5 bonds with positively-charged cations (for example, Nat), even after the direct current pulsing step. Thus the composition remains non-caustic and dermal-friendly after charging, but the increased polarity makes the composition sufficiently reactive to disrupt other covalent bonds. This preference for an ammonium salt notwithstanding, non-ammonium salts 10 which disassociate into anions that behave similarly to NH2- may prove suitable, especially in applications where a non-ammonium salt brings additional benefits. [00071] Second, we found selecting a salt with the same or similar anion to the base (for example, OH-) was preferable over those with dissimilar 15 anions. We believe that with a more homogenous the solution, there will be fewer undesirable side reactions. However, selecting a base and salt with dissimilar anions may nonetheless prove suitable, especially in applications where the dissimilar anion of the salt brings additional benefits. Thus, using these guidelines, by way of example and not 20 limitation, the preferred hydroxide salt for each of the strong bases listed above is ammonium hydroxide. [00072] Finally, while we specifically note the use of the modified base/salt composition in the context of effecting covalent bonds, our inventive composition is not limited to such anti-microbiological 25 uses. Indeed, we believe that our inventive composition may prove useful in any application where a reactive alkali-based composition is needed, but where the composition must be non-caustic and dermal-friendly. For example, we believe that the composition would be useful in preventing and treating mold and fungus, 30 prevention of rust, and lowering the water activity on products such as dried pet foods, ready-to-eat meals, drying paper, and WO 2013/106455 PCT/US2013/020864 19 manufacture of soaps and detergents. [00073] While specific embodiments have been illustrated and described, numerous modifications come to mind without significantly departing from the spirit of the invention and the scope of protection is embodied by 5 the scope of the accompanying claims.
    权利要求:
    Claims (25)
    [1] 1. A method for producing a modified acid/ salt solution, comprising: subjecting a starting solution of an acid and a salt to at least one pulsing 5 event, wherein said pulsing event comprises at least one pulse of direct current; and modifying the starting solution to produce a modified solution having a higher conductivity and higher proton count than the starting solution.
    [2] 2. The method of claim 1, wherein the pulse ranges from 1 to 20 amps at 4 to 16 10 volts and lasts between 5 to 60 seconds.
    [3] 3. The method of claim 1, wherein the pulsing event comprises passing at least one additional pulse of direct current through the starting solution.
    [4] 4. The method of claim 3, wherein the time interval between pulses in a pulsing event ranges from 5 to 60 seconds. 15
    [5] 5. The method of claim 1 further comprising subjecting the solution to an additional pulsing event.
    [6] 6. The method of claim 5, wherein the solution is subjected to pulsing for a length of time ranging from 20 to 70 minutes.
    [7] 7. The method of claim 1, wherein the number of pulsing events ranges from I to 5. 20
    [8] 8. The method of claim 1 further comprising cooling the starting solution to at least 52 0 C after each pulsing event.
    [9] 9. The method of claim 1, wherein the modified solution has a conductivity of between 250 and 1500 mV, a proton count of between 0.95 x 10 2 5 and 1.5 x 10 and a pH of under 3.5. WO 2013/106455 PCT/US2013/020864 21
    [10] 10. The method of claim 1, wherein the acid is hydrochloric acid that is about 50% concentrated, the s alt is ammonium chloride and is about 99% pure, and the acid and salt are combined at about a 6 to 1 ratio by weight.
    [11] 11. The method of claim 1, wherein the s alt is a chloride salt selected from the group 5 consisting of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, aluminum chloride, zinc chloride, nickel chloride, lead chloride, copper chloride, ferrous chloride, ferric chloride gold chloride and combinations thereof.
    [12] 12. The method of claim 1, wherein the salt is a chlorite salt selected from the group consisting of sodium chlorite, potassium chlorite, calcium chlorite, ammonium chlorite, 10 magnesium chlorite, aluminum chlorite and combinations thereof.
    [13] 13. A method for producing a modified base/ salt solution, comprising: subjecting a starting solution of an base and a salt to at least one pulsing event, wherein said pulsing event comprises at least one pulse of direct current; and 15 modifying the starting solution to produce a modified solution having a higher conductivity and higher proton count than the starting solution.
    [14] 14. The method of claim 13, wherein the pulse ranges from 1 to 20 amps at 4 to 16 volts and lasts between 5 to 60 seconds.
    [15] 15. The method of claim 13 further comprising passing at least one additional pulse 20 of direct current through the starting solution.
    [16] 16. The method of claim 15, wherein the time interval between pulses in a pulsing event ranges from 5 to 60 seconds.
    [17] 17. The method of claim 13 further comprising subjecting the solution to an additional pulsing event. 25
    [18] 18. The method of claim 17, wherein the solution is subjected to pulsing for a length WO 2013/106455 PCT/US2013/020864 22 of time ranging from 20 to 70 minutes.
    [19] 19. The method of claim 13, wherein the number of pulsing events ranges from 1 to 5.
    [20] 20. The method of claim 13 further comprising cooling the starting solution to at least 5 52'C after each pulsing event.
    [21] 21. The method of claim 13, wherein the modified solution has a conductivity of no greater than 100 mV, a proton count of between 0.95 x 10 2 4 and 2.8 x 10 6 and a pH of 10.1 or greater.
    [22] 22. The method of claim 13, wherein the base is sodium hydroxide that is about 50% 10 concentrated, the s alt is ammonium hydroxide containing no more than 44% w/w of ammonia, and the base and salt are combined at about a 4 to 1 ratio by weight.
    [23] 23. The method of claim 13, wherein the base is selected from the group consisting of sodium hydroxide, lithium hydroxide (LiOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH), cesium hydroxide (CsOH), calcium hydroxide 15 (Ca(OH) 2 ), strontium hydroxide (Sr(OH) 2 ), barium hydroxide (Ba(OH) 2 ), magnesium hydroxide (Mg(OH) 2 ) and combinations thereof.
    [24] 24. The method of claim 13, wherein the salt is selected from the group consisting of ammonium hydroxide, ammonium nitrate, ammonium carbonate, ammonium chloride and combinations thereof. 20
    [25] 25. The method of claim 13, wherein the salt is ammonium hydroxide.
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    同族专利:
    公开号 | 公开日
    CN104159846A|2014-11-19|
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    EP2802530A4|2015-07-22|
    US20130175478A1|2013-07-11|
    EP2802530A1|2014-11-19|
    CA2863206A1|2013-07-18|
    AU2013208049B2|2016-01-07|
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    法律状态:
    2016-05-05| FGA| Letters patent sealed or granted (standard patent)|
    2020-08-06| MK14| Patent ceased section 143(a) (annual fees not paid) or expired|
    优先权:
    申请号 | 申请日 | 专利标题
    US13/346,160||2012-01-09||
    US13/346,160|US20130175478A1|2012-01-09|2012-01-09|Reactive, non-corrosive, and dermal-friendly composition and methods for manufacturing|
    PCT/US2013/020864|WO2013106455A1|2012-01-09|2013-01-09|Reactive, non-corrosive and dermal-friendly compositions and methods|
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