HK1073618B - Enhanced formulations for neutralization of chemical, biological and industrial toxants - Google Patents
Enhanced formulations for neutralization of chemical, biological and industrial toxants Download PDFInfo
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Description
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is U.S. patent application Ser. No. 09/607,586 entitled "formulations for neutralizing chemical and biological toxants" filed at 29.6.2000, now filed on part of U.S. Pat. No. 6,566,574, and U.S. patent application Ser. No. 09/607,586 filed at 30.6.1998, filed on part of U.S. patent application Ser. No. 09/109,235 entitled "aqueous foams for mitigation and decontamination of chemical and biological warfare agents", and claims the benefit of U.S. provisional patent application Ser. No. 60/146,432 filed at 29.7.1999, the specification of which is incorporated herein by reference.
This application is also U.S. patent application Ser. No. 09/952,940 entitled concentrated formulations and methods for neutralizing chemical and biological toxants, filed on 9/14/2001, now a continuation-in-part of patent publication No. 2003/060517, and U.S. patent application Ser. No. 09/952,940 is a continuation-in-part of U.S. patent application Ser. No. 09/607,586 filed on 6/29/2000, entitled formulations for neutralizing chemical and biological toxants, the specification of which is incorporated herein by reference.
The present application claims the benefit of U.S. provisional patent application serial No. 60/326,508 entitled "DF-200, an enhanced formulation for decontamination and mitigation of CBW agents and biological pathogens" filed on day 10/1 of 2001 and U.S. provisional patent application serial No. 60/334,271 entitled "configuration for rapid DF-200 deployment" (filed on day 11/30 of 2001) and U.S. provisional patent application serial No. 60/387,104 entitled "decontamination formulation" filed on day 6/7 of 2002, the descriptions of which are incorporated herein by reference.
Government rights
The invention is entitled to the government of contract number DE-AC04-94AL85000 awarded by the U.S. department of energy.
Background
Field of the invention (technical field):
the present invention relates to formulations for neutralizing chemical, biological and industrial toxants.
Background：
The present invention relates to materials and methods for neutralizing toxic chemical, biological and industrial compounds or agents, particularly chemical and biological warfare agents, and methods of making the same. In particular, the present invention relates to materials comprising solubilizing compounds, reactive compounds and bleach activators, which may be delivered in the form of foams, sprays, liquids, mists and aerosols to enhance the rate of reaction leading to neutralization of chemical compounds, and other additives used to kill or attenuate certain biological compounds or agents.
Terrorist threats, which may involve weapons of mass destruction, are increasing both in the united states and abroad. The use, and threat of use, of chemical and biological agents in the context of weapons of mass destruction are of great importance to national defense and national and local law enforcement.
Certain chemical warfare ("CW") agents known to pose a threat by terrorists share chemistry that provides opportunities for developing countermeasures. The chemical agents sarin, 1, 2, 2-trimethylpropyl methylphosphonyl fluoride, and tabun (G-formulation) are all examples of phosphorus-containing compounds that can lose their toxicity when chemically altered. Examples of H-reagents mustard, and of V-reagents VX can also be chemically altered and rendered harmless. In addition, certain known BW agents, including botulinum toxin, anthrax and other Bacillus species, asexual bacteria, including plague and various viruses, may also be chemically inactivated.
CW or biological warfare ("BW") attacks may involve the local placement or widespread dissemination of an agent or agents to affect a population of human individuals. Because of the flexibility with which CW and BW ("CBW") agents can be used, responders may encounter formulations in a variety of physical states including bulk, aerosol and vapor.
There is a need for an effective, rapid and safe (non-toxic and non-corrosive) decontamination technique to restore civilian facilities in the event of a domestic terrorist attack. Ideally, the technology would be suitable for use in a variety of situations such as open, semi-enclosed and enclosed installations and decontamination of sensitive equipment. Examples of types of facilities where decontamination formulations may be used include stadiums (open), and underground subway stations (semi-enclosed), and air stations (airport terminal) or office buildings (enclosed). The foam form can be used to extend the contact time of the formulation on a vertical surface.
Decontamination of chemical compounds has focused primarily on chemical warfare agents, particularly on nerve agents (e.g., G and V agents) and on vesicants (e.g., mustard, or simply mustard). Reactions involving detoxification of chemical agents can be divided into substitution and oxidation reactions. Decontamination of biological agents is primarily focused on bacterial spores (e.g., anthrax), which are considered to be the most difficult to kill of all microorganisms. Additional background is discussed in U.S. patent application serial nos. 09/607,586 and 09/952,940.
There is also a need for rapid, safe and effective neutralization of toxic industrial chemicals such as malathion, hydrogen cyanide, sodium cyanide, butyl isocyanate, carbon disulfide and phosgene.
U.S. patent application Ser. No. 09/607,586 is generally related to water-based purification techniques ("DF-100") for the rapid neutralization of chemical and biological warfare ("CBW") agents. The preparation comprises the following components:
● are effective for neutralizing chemical and biological agents;
● are environmentally benign (i.e., non-toxic and non-corrosive);
● function on many contemplated material surfaces; and
● may be incorporated into a wide variety of carriers (e.g., foams, liquid sprays, mists) that serve a wide variety of handling purposes.
The primary interest in using this technology is from the first responders (e.g., fire brigade, police, and hazardous materials units) in folks, which will arrive first at the scene of an attack using CBW agents, followed by a secondary interest in using this agent for facility restoration. DF-100 presents a technical problem, and the first responders in folk life use the formulation less optimally. These technical problems include: (1) the pH of DF-100 must be adjusted to optimally decontaminate each specific chemical and biological agent. In other words, different formulations may be required to neutralize each particular agent. While it is relatively simple to adjust the pH of the formulation in the laboratory, it is more difficult in the field and is generally not suitable for the primary user of the technology (i.e. first responders). (2) The reaction rate of mustard for one chemical agent is relatively slow compared to the reaction rate for the other chemical agent.
These technical problems limit the effectiveness of DF-100 in practical applications. An improved formulation, DF-100A, is disclosed in U.S. patent application serial No. 09/952,940, addressing the need to adjust the pH for each particular agent (i.e., the first technical problem described above). However, while DF-100A does not improve upon formulation performance at a single pH, it does not completely solve the problem, and even does not address the second technical problem (i.e., relatively low reaction rate with mustard). Additionally, some forms of DF-100/100a may use short chain alcohols (e.g., isobutanol, isopropanol), which can cause flammability problems if the formulation is packaged in concentrated form. Additionally, some forms of DF-100/100a may use diethylene glycol monobutyl ether (DEGMEB), which may cause false alarms on some chemical agent sensors and detectors, particularly older sensors used in some military settings.
As a point of comparison, the following are examples of preferred formulations for DF-100:
DF-100
2.6% Variquat80MC (cationic surfactant)
3.3% Methyltrialkylammonium chloride 477 (cationic hydrotrope)
0.8% of 1-dodecanol (aliphatic alcohol)
0.5% isobutanol (short chain alcohol)
1.6% Isopropanol (short chain alcohol)
0.1% guar gum type flocculant 8000 (cationic polymer)
1.6% diethylene glycol monobutyl ether (solvent)
4% sodium bicarbonate (buffer and peroxide activator)
4% Hydrogen peroxide (liquid oxidizing agent)
75% water
The preparation can be adjusted to pH 8 for optimal decontamination of mustard and anthrax spores; and can be adjusted to a pH of 10.5 for optimal purification of VX.
The decontamination of the chemical agent is generally effective anywhere between pH 8 and 10.
As another comparison, the following are examples of preferred formulations for DF-100A:
DF-100A
5.3% Variquat80MC (cationic surfactant)
2.8% methyltrialkylammonium chloride 477 (cationic hydrotrope)
0.65% of 1-dodecanol (aliphatic alcohol)
0.6% isobutanol (short chain alcohol)
0.1% guar gum type flocculant 8000 (cationic polymer)
1.35% diethylene glycol monobutyl ether (solvent)
4% Potassium bicarbonate (buffer and peroxide activator)
4% Hydrogen peroxide (oxidant)
81% water
The preparation can be adjusted to pH 8 for optimal decontamination of mustard and anthrax spores; and can be adjusted to a pH of 10 for optimal purification of VX. The decontamination of the chemical agent is generally effective anywhere between pH 8 and 10. In addition, it can be adjusted to a pH of 9.2 to less optimally decontaminate all reagents.
In both examples shown above for DF-100 and DF-100A, hydrogen peroxide and bicarbonate react to produce a highly reactive negatively charged nucleophile, Hydroperoxycarbonate (HCO)4 -) It is a strong oxidant. Other negatively charged nucleophiles are formed by using hydrogen peroxide, including: hydroxyl ion (OH)-) And hydroperoxide ion (OOH)-). The function of the other components of these formulations is discussed in detail in U.S. patent application Ser. Nos. 09/607,586 and 09/952,940.
The present invention provides enhanced cleaning formulations (commonly referred to as "DF-200") comprising bleach activators, which result in faster reaction kinetics, improved performance, and the elimination required for pH adjustment. Although bleach activators are routinely used in (anionic) laundry detergents, the present invention can use them with cationic surfactants, and where good solubility of the activator in water is useful to achieve rapid reaction times. Desirable bleach activators for use in the present invention are preferably water soluble, non-toxic, non-flammable, and low cost.
Pentaglucose acetate is an O-acetyl peroxide activator, which has been used as an activator in a bactericidal composition containing a cationic surfactant and an inorganic peroxide (see japanese laid-open patent publication No. 62-155203(1987) entitled "bactericidal composition for cowsheds"). Penta-acetic acid glucose ester is a solid at room temperature (i.e., melting point 110 ℃) and is insoluble in water. In an aqueous solution containing peroxide, it dissolves very slowly in water as it reacts with the peroxide. At a concentration of about 2% glucose pentaacetate, several hours are required to dissolve. Which makes its use undesirable for a fast deployment configuration.
Summary of the invention (summary of the invention)
The present invention relates to a formulation for neutralizing at least one poison, comprising: at least two solubilizing compounds, wherein at least one solubilizing compound is a cationic surfactant and at least one solubilizing compound is a cationic hydrotrope; at least one reactive compound, wherein the at least one reactive compound is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, hydroperoxycarbonate, peracetic acid, sodium perborate, sodium pyrophosphate peroxide, sodium peroxysilicate, and sodium percarbonate; and at least one bleach activator selected from the group consisting of O-acetyl, N-acetyl, and nitrile based bleach activators; wherein the at least one toxicant is neutralized by the at least two solubilizing compounds, the at least one reactive compound and the at least one bleach activator when mixed with water and exposed to the at least one toxicant. In a preferred embodiment, the cationic surfactant comprises a quaternary ammonium salt, most preferably cetyltrimethylammonium bromide, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyldimethylbenzylammonium salts, tetrabutylammonium bromide, or WITCO VARIQUAT80MCTMOr a combination thereof. The formulation may additionally comprise a water-soluble polymer, preferably polyvinyl alcohol, guar gum, (cationic or non-ionic) polydiallyldimethylammonium chloride, polyacrylamide, poly (ethylene oxide), glycerol, polyethylene glycol 8000(PEG8000), or guar-type flocculant 8000TM(guar 2-hydroxypropyl ether), or a combination thereof. The formulation may further comprise an aliphatic alcohol having 8 to 20 carbon atoms per molecule, a solvent (preferably di (propylene glycol) methyl ether or diethylene glycol monobutyl ether, or a combination thereof), and/or a carbonate salt (preferably potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, lithium bicarbonate, ammonium carbonate, or potassium carbonate, or a combination thereof). The bleach activator is preferably water soluble, most preferably acetylcholine chloride, monoacetin (glycerol monoacetate), diacetin (glycerol diacetate), 4-cyanobenzoic acid, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, ethylene glycolMethyl formate, dimethyl glutarate, diethylene glycol monoethyl ether acetate, glycerol diacetate (diacetin), glycerol monoacetate, glycerol triacetate, or propylene glycol diacetate, or combinations thereof. Alternatively, the bleach activator may be water soluble, preferably Tetraacetylethylenediamine (TAED), N-Nonanoyloxybenzenesulfonate (NOBS), or N-acetylglucosamine, or a combination thereof. When mixed with water, the formulation preferably has a pH of about 9.6 to about 9.8. One embodiment of the present invention consists essentially of 1-10% benzalkonium chloride, 1-8% propylene glycol diacetate; 1-16% hydrogen peroxide; and 2-8% of potassium bicarbonate.
The present invention also relates to a formulation for neutralizing at least one poison, comprising: at least one cationic surfactant; at least one reactive compound, wherein the at least one reactive compound is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, hydroperoxycarbonates, peracetic acid, sodium perborate, sodium pyrophosphate peroxyhydrate, sodium peroxysilicate, and sodium percarbonate; at least one bleach activator selected from the group consisting of O-acetyl, N-acetyl, and nitrile based bleach activators; and at least one carbonate salt which is not one of the at least one reactive compound; wherein the at least one surfactant, the at least one reactive compound, the at least one bleach activator, and the at least one carbonate, when mixed with water and exposed to the at least one toxicant, neutralize the at least one toxicant. In a preferred embodiment, the formulation has a pH of about 9.6 to about 9.8 when mixed with water and the cationic surfactant comprises a quaternary ammonium salt, most preferably benzalkonium chloride. The at least one carbonate salt is preferably potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, lithium bicarbonate, ammonium carbonate, or potassium carbonate, or a combination thereof. One embodiment consists essentially of at least one cationic surfactant, at least one reactive compound, at least one bleach activator, and at least one carbonate salt. The bleach activator is preferably water soluble, most preferably acetylcholine chloride, monoacetin (glycerol monoacetate), diacetin (glycerol diacetate), 4-cyanobenzoic acid, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate, glycerol diacetate (diacetin), glycerol monoacetate, glycerol triacetate, or propylene glycol diacetate, or combinations thereof.
The invention further relates to a formulation for neutralizing at least one poison, comprising: at least one cationic surfactant; at least one reactive compound, wherein the at least one reactive compound is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, hydroperoxycarbonates, peracetic acid, sodium perborate, sodium pyrophosphate peroxyhydrate, sodium peroxysilicate, and sodium percarbonate; at least one water-soluble bleach activator selected from the group consisting of O-acetyl, N-acetyl, and nitrile-based bleach activators; wherein the at least one surfactant, the at least one reactive compound, and the at least one water-soluble bleach activator, when mixed with water and exposed to the at least one toxicant, neutralize the at least one toxicant. In a preferred embodiment, the at least one water-soluble bleach activator is acetylcholine chloride, monoacetin (glycerol monoacetate), diacetin (glycerol diacetate), 4-cyanobenzoic acid, ethylene glycol diacetate, propylene glycol monomethyl ether acetate, methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate, glycerol diacetate (diacetin), glycerol monoacetate, glycerol triacetate, or propylene glycol diacetate, or a combination thereof. The cationic surfactant preferably comprises a quaternary ammonium salt, most preferably benzalkonium chloride. The formulation preferably additionally comprises at least one carbonate salt, most preferably potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, lithium bicarbonate, ammonium carbonate, or potassium carbonate, or a combination thereof. When mixed with water, the formulation has a pH of about 9.6 to about 9.8. One embodiment consists essentially of at least one cationic surfactant, at least one reactive compound, and at least one water-soluble bleach activator.
The invention further relates to a formulation for neutralizing at least one poison, comprising: at least one solubilizing compound selected from the group consisting of cationic hydrotropes and aliphatic alcohols containing 8 to 20 carbon atoms per molecule; at least one reactive compound, wherein the at least one reactive compound is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, hydroperoxycarbonates, peracetic acid, sodium perborate, sodium pyrophosphate peroxyhydrate, sodium peroxysilicate, and sodium percarbonate; and at least one bleach activator selected from the group consisting of O-acetyl, N-acetyl, and nitrile based bleach activators; wherein the at least one solubilizing compound, the at least one reactive compound, and the at least one bleach activator, when mixed with water and exposed to the at least one toxicant, neutralize the at least one toxicant.
The invention also relates to any one of the above formulations packaged into a kit. In a first embodiment, a kit comprises: a premix component comprising at least 2 solubilizers; a first component comprising at least one bleach activator; and a second component comprising at least one reactive compound. The first embodiment may additionally comprise water and a base, the premix component may additionally comprise a water soluble polymer, the at least one bleach activator is preferably propylene glycol diacetate, glycerol diacetate, and/or TAED, the premix component may additionally comprise an aliphatic alcohol containing from 8 to 20 carbon atoms per molecule, with respect to the second component comprising at least one reactive compound, the at least one reactive compound may be urea hydrogen peroxide, said second component additionally comprises sodium percarbonate, the premix component may additionally comprise a short chain alcohol. A second embodiment comprises: a first premix component comprising at least 2 solubilizers and water; and a second premix component comprising at least one bleaching compound and at least one reactive compound, wherein at least one bleach activator is in a solid state. In a second embodiment, the first premix component preferably additionally comprises an acid, the at least one bleach activator preferably comprises acetylcholine chloride, the at least one reactive compound comprises urea hydrogen peroxide and the at least one bleach activator comprises TAED, the at least one bleach activator being encapsulated to prevent premature reaction with the at least one reactive compound. A third embodiment comprises: a premix component comprising at least 2 solubilizers and at least one bleach activator; and a component comprising at least one reactive compound. In a third embodiment, the premix components may additionally comprise water and an acid, the component comprising at least one reactive compound may comprise sodium percarbonate and another acid, and with respect to the component comprising at least one reactive compound additionally comprising a mixture of potassium carbonate and potassium bicarbonate, the at least one reactive compound may comprise urea hydrogen peroxide.
Objects, advantages and novel features, and further scope of applicability of the present invention will be set forth in part in the detailed description to follow, taken in conjunction with the accompanying drawings, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
Brief Description of Drawings
The accompanying drawings, which are incorporated in and form a part of the specification, illustrate one or more embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating one or more preferred embodiments of the invention and are not to be construed as limiting the invention.
In the drawings:
FIG. 1 is a graph showing the effect of DF-200 on the killing of Bacillus subtilis (anthrax mimics) spores;
FIG. 2 is a schematic illustration of a preferred hybrid approach to the first rapid deployment configuration of the present invention ("DF-200 HF rapid deployment"); and
FIG. 3 is a schematic of a preferred mixing process for a second rapid deployment configuration ("DF-200 HF slurry rapid deployment") of the present invention.
Description of the preferred embodiments
(Best Mode for Carrying Out The Invention)
The present invention addresses the need for a general formulation that neutralizes the adverse effects of either or both chemical and biological toxants, where toxants are defined as any chemical or biological compound, component, species, or agent that causes death, temporary incapacitation, or permanent injury to a human or animal if left untreated, or through its chemical or biological effects on a living process. This includes all such chemical or biological agents, regardless of their source or their method of production, regardless of whether they are produced in facilities (facilities), in munitions or elsewhere. Neutralization is defined as moderating, detoxifying, decontaminating, or otherwise destroying the toxicant to the extent that the toxicant no longer causes an acute adverse effect on the human or animal. The formulations of the invention and the variants can be neutralized and do not themselves contain or produce infections, significant adverse health effects, or even death in animals.
An important subset of chemical and biological compounds to which the present invention is directed are chemical warfare ("CW") and biological warfare ("BW") agents. However, the present invention also contemplates toxicants that may cause possible adverse health effects to animals, including humans, wherein such adverse health effects include infection, acute and chronic health effects, and death. These poisons may be found in agricultural facilities, animal or dairy farms, or food processing or packaging facilities. In addition, the present invention addresses the need for formulations that are not toxic and corrosive in nature and that can be delivered in a variety of ways and phases. Certain embodiments are discussed in U.S. patent application Ser. Nos. 09/607,586 and 09/952,940. The present invention provides additional embodiments that differ substantially from the prior art and earlier embodiments, as described below.
The term "formulation" is defined herein as an activated product or solution (e.g., an aqueous solution) that is applied to a surface or body for neutralization, with or without the addition of a foam-producing gas (e.g., air). Unless otherwise specifically indicated, concentrations, components or ingredients set forth herein are weight percentages relative to the total activated solution. The term "water" is defined herein to broadly include: pure water, tap water, de-ionized water, demineralized water, sea water, or primarily H2O and any other liquid.
One example of the minimum component group for DF-200 formulations that can achieve significant spore kill rates comprises four components:
(1) a solubilizing agent selected from the group consisting of cationic surfactants (e.g., Variquat80 MC), cationic hydrotropes (e.g., methyltrialkylammonium chloride 477), and fatty alcohols (e.g., 1-dodecanol);
(2) bleach activators selected from the group consisting of O-acetyl, N-acetyl, and nitrile peroxide activators (e.g., propylene glycol diacetate);
(3) reactive compounds (e.g. hydrogen peroxide, peracetic acid); and
(4) and (3) water.
The solubilizing agent is effective to render the poison susceptible to attack, while the reactive compound is effective to attack and neutralize the poison, the bleach activator enhancing the process.
Examples of suitable cationic surfactants include: quaternary ammonium salts and polymeric quaternary ammonium salts. Examples of suitable quaternary ammonium salts include: cetyltrimethylammonium bromide, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyldimethylbenzylammonium salts, and tetrabutylammonium bromide. Preferably the cationic surfactant is WITCO VARIQUAT80MCTMIt is a mixture of benzyl (C12-C16) alkyl dimethyl ammonium chlorides. The concentration of quaternary ammonium salt used in the DF-200 formulation preferably does not exceed about 10% because quaternary ammonium salts become significantly toxic to humans and the environment at higher concentrations.
Examples of suitable cationic hydrotropes include: tetrapentylammonium bromide, triacetylmethylammonium bromide, and tetrabutylammonium bromide. A preferred cationic hydrotrope is WITCO methyltrialkylammonium chloride 477TMPentamethyltallow trimethylene diammonium dichloride.
Examples of suitable aliphatic alcohols include alcohols containing 8 to 20 carbon atoms per molecule, such as: 1-dodecanol, pure dodecanol, hexadecanol, and 1-tetradecanol.
Examples of suitable bleach activators are discussed subsequently.
Examples of suitable reactive compounds include: a peroxide compound; hydrogen peroxide; urea hydrogen peroxide; sodium perborate; sodium percarbonate; sodium carbonate perhydrate; sodium pyrophosphate peroxide; sodium hydrogen peroxysilicate; peroxide adducts of pyrophosphates; citric acid; sodium sulfate; urea; and sodium silicate; activated peroxide compounds (e.g., hydrogen peroxide + bicarbonate); peracetic acid; oxime salts (e.g., butane-2, 3-dione, monoxime ion, and phenyl hydroxamate); alkoxides (e.g., methoxide and ethoxide); aromatic ethers (e.g., aryl-substituted benzene sulfonates); aldehydes (e.g., glutaraldehyde); a salt of peroxymonosulfate; fenton's reagent (mixture of iron and peroxide); and sodium hypochlorite. The use of these reactive compounds in DF-200 formulations can generate a variety of negatively charged nucleophiles, such as hydroxide ion (OH) when hydrogen peroxide is used-) And hydroperoxide ion (OOH)-) (ii) a And/or produce hydroperoxycarbonate ions (HCO) when hydrogen peroxide is combined with a carbonate4 -). Hydroperoxycarbonate ion (HCO)4 -) Is specific to hydroxyl (OH)-) Or hydroperoxide ion (OOH)-) Much stronger oxidizing agents, particularly effective in reactions with biological poisons. When hydrogen peroxide is used in the DF-200 formulation, its concentration is preferably less than about 10% because higher concentrations, particularly in the 30-50% hydrogen peroxide concentration range, are significantly corrosive.
To obtain extremely high spore kill rates, it is preferred to add a carbonate salt (e.g., sodium bicarbonate or potassium bicarbonate) to the minimum component group described above for the DF-200 formulation. When a peroxide compound (e.g., hydrogen peroxide) is used as the reactive compound for DF-200, the added carbonate combines with, for example, hydrogen peroxide to form a highly reactive Hydroperoxycarbonate (HCO)4 -) A substance. The addition of carbonate may also buffer the formulation to optimize pH.
Thus, for a DF-200 formulation that can achieve very high spore kill rates, the minimum component group can contain 5 components:
(1) a solubilizing agent selected from the group consisting of cationic surfactants (e.g., Variquat80 MC), cationic hydrotropes (e.g., methyltrialkylammonium chloride 477), and fatty alcohols (e.g., 1-dodecanol);
(2) bleach activators selected from the group consisting of O-acetyl, N-acetyl, and nitrile peroxide activators (e.g., propylene glycol diacetate);
(3) reactive compounds (e.g., hydrogen peroxide, peracetic acid, etc.);
(4) carbonates (e.g., sodium bicarbonate); and
(5) and (3) water.
Examples of suitable carbonates include: potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, lithium bicarbonate, ammonium carbonate, and potassium carbonate.
FIG. 1 shows the results of purification of Bacillus subtilis spores (initial concentration 10)7Spores/ml). Spores were exposed to 4 different sub-combinations (subcombining) of the various components of the DF-200 formulation for 1 hour (pH of the formulation was 9.8). The extent of spore kill was determined by culturing surviving organisms. As shown in fig. 3, significant spore killing was achieved by using 2 different combinations: (1) 2% Variquat (cationic surfactant), 2% propylene glycol diacetate (bleach activator), and 2% hydrogen peroxide (oxidant) in water and (2) 2% Variquat (cationic surfactant), 5% potassium bicarbonate (buffer and peroxide activator), and 2% hydrogen peroxide (oxidant) in water. However, very high spore kill was achieved by using a third combination comprising (3) an aqueous solution of 2% Variquat (cationic surfactant), 2% propylene glycol diacetate (bleach activator), 5% potassium bicarbonate (buffer and peroxide activator) and 2% hydrogen peroxide (oxidant).
Next, various alternative embodiments and configurations of DF-200 formulations will be provided.
DF-200HF (high foam)
The present invention provides enhanced decontamination formulations ("DF-200 HF") suitable for high foam applications. One example of a DF-200HF formulation comprises:
DF-200HF (high foam)
1-4% (preferably 2%) Variquat80MC (cationic surfactant)
0.5-3% (preferably 1%) methyltrialkylammonium chloride 477 (cationic hydrotrope)
0.2-0.8% (preferably 0.4%) 1-dodecanol (aliphatic alcohol)
0.05-0.1% of guar gum type flocculant 8000 (cationic water-soluble polymer)
0.5% bis (propylene glycol) methyl ether (solvent)
0.1-10% (preferably 1-4%) hydrogen peroxide (oxidant)
0.1-10% (preferably 2-8%) bicarbonate (buffer and peroxide activator)
1-4% propylene glycol diacetate (bleach activator)
67-97% of water
The formulation is effective at a pH between 7.5 and 10.5. The formulation can be adjusted to a pH between 9.6-9.8 to optimally decontaminate all target agents. The "high-foaming" formulation includes a cationic water-soluble polymer (e.g., a guar-based flocculant 8000)TM) Which increases the bulk viscosity of the solution and produces a more stable foam.
Examples of suitable non-anionic water-soluble polymers include: polyvinyl alcohol, guar gum, (cationic or nonionic) polydiallyldimethylammonium chloride, polyacrylamide, polyethylene glycol 8000(PEG8000), and guar gum-based flocculants 8000TM(guar 2-hydroxypropyl ether). Cationic polymers are preferred over nonionic polymers; anionic polymers are not effective. Fatty alcohol 1-dodecanol for increasing the surface of foam layerViscosity, and also improves foam stability against drainage and bubble collapse.
DF-200LF (Low foam)
The present invention provides enhanced cleansing formulations ("DF-200 LF") suitable for low foaming applications. One example of a DF-200HF formulation comprises:
DF-200HF (Low foam)
4% Variquat80MC (cationic surfactant)
0.4% lauramide DEA [ N, N-bis (2-hydroxyethyl) -dodecanamide ] (foam booster)
1-4% propylene glycol diacetate (bleach activator)
0.5% bis (propylene glycol) methyl ether (solvent)
0.05-0.1% of guar gum type flocculant 8000 polymer (cationic water-soluble polymer)
0.1-10% (preferably 1-4%) hydrogen peroxide (oxidant)
0.1-10% (preferably 2-8%) bicarbonate (buffer and peroxide activator)
71-94% of water
The formulation is generally effective at a pH between 7.5 and 10.5. The formulation can be adjusted to a pH between about 9.6-9.8 to optimally decontaminate all of the target agent.
The term "high foam" refers to the ability of a formulation to form a highly stable and long lasting foam, while a "low foam" formulation forms a much less stable foam. The following tables show the improved performance of DF-200HF and DF-200LF as compared to DF-100A. The symbol "ND" refers to a concentration below the detectable limit and "PGD" refers to propylene glycol diacetate (a preferred bleach activator).
Table 1: summary of reaction rates for mustard simulants (2-chloroethylphenylsulfide)
Table 2: summary of reaction rates for VX mimetics (o-Ethyl S-ethylphenylthiophosphonate)
Table 3: summary of reaction rates for G reagent simulant (diphenylphosphoryl chloride)
Table 4: summary of killing rates for anthrax mimetics (Bacillus subtilis spores)
The differences between formulations DF-200 and DF-100/100A included:
DF-200 is active against all agents at a single pH. The formulation is effective at a pH between about 7.5 and 10.5; more effective at a pH between about 9.2 and 9.8; most effective at a pH value between about pH 9.6 and 9.8;
DF-200 has better performance on mustard;
DF-200 has better performance on bacterial spores;
DF-200 has lower concentrations of cationic surfactant and/or cationic hydrotrope, which further reduces the toxic and corrosive properties of the formulation (already low);
DF-200 has a lower concentration of foam stabilizing component, 1-dodecanol;
DF-200 does not use short chain alcohols (e.g., isobutanol, isopropanol), which cause flammability problems when the formulation is packaged in concentrated form;
DF-200 does not use diethylene glycol monobutyl ether (DEGMBE), which can cause false alarms on some chemical sensors and detectors, particularly older sensors used in some military facilities; and
DF-200 can contain lower concentrations of hydrogen peroxide, which also reduces the (already low) toxic and corrosive properties of the formulation.
Additional differences between DF-200 and DF-100A include:
DF-200 is best used at higher pH (about 9.6-9.8) than DF 100A.
Note, however, that this is a typical pH for conventional household products such as laundry detergents, shampoos, and dishwashing detergents; and
DF-200 has more individual components (e.g. hydrogen peroxide and bleach activator) than DF-100A (where there is only one component and hydrogen peroxide should be kept separate) which should be kept separate from the main formulation until used. This will be discussed in more detail below.
One reason that DF-200 formulations (e.g., DF-200HF and DF-200LF) perform better than DF-100 and DF-100A formulations is the addition of a bleach activator (e.g., propylene glycol diacetate). The bleach activators may be compounds containing O-or N-bound acetyl groups which are bound to strongly nucleophilic hydroperoxy anions (OOH)-) The reaction produces peroxygen-generating species, which are more efficient oxidants than hydrogen peroxide alone.
Since the 50's of the 20 th century, many different bleach activators have been used in commercial laundry detergents, as well as other commercial products. The most commonly used activator is Tetraacetylethylenediamine (TAED), which is used primarily in europe and asia; and n-Nonanoyloxybenzenesulfonate (NOBS), which is used primarily in the united states. NOBS is a chemical proprietary to Proctor & Gamble. In laundry detergents, hydrogen peroxide is provided in solid form (usually as sodium perborate, which reacts in water to form a hydroperoxyl anion). The addition of bleach activators greatly enhances the ability of laundry detergents to remove stains from clothes.
It should be noted that TAED and NOBS bleach activators are extremely insoluble in water (e.g., TAED is only 0.1% soluble at 25 ℃). To overcome this problem in laundry detergents, solid TAED or NOBS particles are kept in suspension by the agitation of the washing machine, where they react slowly with the hydrogen peroxide in the detergent. However, agitation in the DF-200 formulation poses practical problems; therefore, water-soluble bleach activators are preferred.
Useful water-soluble bleach activators include short-chain organic compounds containing ester linkages, such as ethylene glycol diacetate, propylene glycol monomethyl ether acetate, methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate, glycerol diacetate (diacetin), glycerol monoacetate, glycerol triacetate, and propylene glycol diacetate. The preferred water soluble bleach activator is Propylene Glycol Diacetate (PGD), as shown below:
the molecule is conjugated with a hydroperoxyl anion (OOH)-) The reaction was interrupted and the ester linkage was interrupted to form 2 peroxy-generating molecules.
Propylene glycol diacetate also acts as an organic solvent, being highly effective in solubilizing insoluble organic molecules such as chemical warfare agents, and foam stabilizers/boosters such as 1-dodecanol and lauramide DEA. Thus, the added function of this compound is that it can be used to supplement the diethylene glycol monobutyl ether (DEGMBE) solvent used in DF-100 and DF-100A, or to supplement the di (propylene glycol) methyl ether solvent used in some DF-200 formulations, thereby allowing propylene glycol diacetate to be used for dual purposes (i.e., solvent and bleach activator).
Bleach activators are generally unstable in water for extended periods of time. This is particularly true when the aqueous solution is at a high pH (> 10). Thus, for long shelf life, the propylene glycol diacetate (or other bleach activator) is preferably stored separately from the aqueous solution until use. This is unlike other products that use bleach activators (e.g., laundry detergents) where all formulation components are kept dry and separate until use (in the case of laundry detergents, the bleach activator is sealed to prevent it from reacting with the peroxide component until the two components are mixed in water).
Another example of a water soluble bleach activator is ethylene glycol diacetate, which works well in DF-200 formulations. However, when ethylene glycol diacetate reacts with hydrogen peroxide, it forms ethylene glycol (i.e., antifreeze), which is a relatively toxic by-product. Propylene glycol diacetate, on the other hand, does not form such a relatively toxic by-product.
DF-200NF (bubble-free)
The present invention also relates to a non-foaming embodiment ("DF-200 NF") that may be used in specific applications, such as killing biological organisms, batch processing (e.g., during neutralization of chemical disarmed items, i.e., in a bath of solution), or spray applications. Preferred examples of such formulations comprise (illustrative amounts):
DF-200NF (No bubble)
1-10% (preferably 2.5%) benzalkonium chloride (cationic surfactant)
1-8% propylene glycol diacetate (bleach activator)
1-16% hydrogen peroxide (oxidant)
2-8% potassium bicarbonate (buffer and peroxide activator)
65.5-93.5% of water
The formulation can be adjusted to a pH of about 9.6-9.8 to achieve optimum performance, effective for decontamination of all target agents.
DF-100E
The present invention also relates to an enhanced form of DF-100A which uses a propylene glycol diacetate bleach activator. A preferred embodiment of the enhancement formulation, ("DF-100E") comprises (in illustrative amounts):
DF-100E
5.3％Variquat 80MC
2.8% Methyltrialkylammonium chloride 477
0.65% of 1-dodecanol
0.5% isobutanol
0.1% guar gum type flocculant 8000
1.35% diethylene glycol monobutyl ether
2-8% of bicarbonate
1-4% hydrogen peroxide
1-4% propylene glycol diacetate
73-85% of water
The formulation can be adjusted to a pH of about 9.6-9.8 to achieve optimum performance for all agents. DF-100E (2% PGD/3.00% H)2O23.75% bicarbonate) versus chemical simulant the following table 5 shows:
table 5: summary of the reaction rates for the DF-100E formulation in the kinetic experiments.
Experiments with anthrax spore mimics (Bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after 30 minutes of exposure to DF-100E.
Other bleach activators such as water insoluble NOBS or TAED may be used in place of propylene glycol diacetate in DF-100E. However, as noted above, this results in a slurry mixture rather than a true liquid solution.
The following table summarizes some of the differences between DF-100, DF-100A, DF-100E, DF-200HF, DF-200LF, DF-200NF, and DF-200HF slurries:
table 6: comparison of various decontamination formulations
Kit configuration
In the following section, various examples of 2-part, 3-part, and 4-part "kit" configurations for different embodiments of the DF-200 formulation are shown. Typically 2-part and 3-part kits have a large amount of water (typically a foam component) already "prepackaged" in one of two (or 3) containers. This allows for rapid deployment of the decontamination solution, the use of small devices (e.g. backpack), and does not require any additional water to be provided in the field.
In contrast, 4-part kits typically require the addition of make-up water at or near the point of contamination in the field. This makes the "package" containing the other 3 parts much lighter, making it easier to ship and store. However, a source of compensation (which may be seawater) is required in the field.
In general, depending on the application, DF-200 formulations may be formulated in two ways, with or without the use of "prepackaged" bulk water.
DF-200HF (kit configuration)
The DF-200HF formulations can be configured as a 4-part kit, then prepared for field use (illustrative amounts) as follows:
DF-200HF (4-part kit)
Part A (foam concentrate)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
4 gb-dodecanol
1g of Karl-type flocculant 8000 Polymer
5g of di (propylene glycol) methyl ether
7.5g of potassium bicarbonate
141g of water
Part B (solid component)：
50g of sodium percarbonate
50g of carbamide peroxide
Part C (Bleach activator)：
20g of propylene glycol diacetate
Part D (Water for Compensation)：
800g of water
In this example of a 4-part configuration, a large amount of water is not included in the "package" (i.e., parts a, B, and C), which minimizes the weight of the package for shipping and storage. Here, the make-up water (part D) will be in placeProvided in the field at or near the site of contamination. The pH of the formulation can be adjusted to between about 9.6 and 9.8 for optimum performance. The formulation described above will produce 1 liter of "high" bubble solution. In this example, sodium percarbonate provides part of the hydrogen peroxide, part of the bicarbonate, and the base for the buffer solution. The remaining hydrogen peroxide is provided by urea hydrogen peroxide. The total hydrogen peroxide concentration in this example is about 3%. The viscosity of the preparation can be adjusted to about 4-9mm2/s。
Various methods can be used in the field to mix DF-200HF formulations configured as 4-part kits, for example:
method 1: make-up water (part D) is provided. Then, part B is mixed into part D. Then, the parts C and a are added to the part B + D. Preferably within 8 hours.
Method 2: mix part C into part a. Make-up water (part D) is provided. Then, part B is mixed into part D. Kept separate until use. When required for use, part a + C is mixed into part B + D. Preferably within 8 hours of the start of mixing the parts A + C into the parts B + D.
In general, it is preferred to use activated DF-200 formulations within 8 hours after mixing, however, they may also be effective for up to 24 hours and longer. DF-200HF (high foam) can be applied to a surface for a long period of time and then rinsed off. However, DF-200LF (Low foam) may be used in a manner different from the DF-100/100A and DF-200HF formulations. Rather than leaving the DF-200LF on the surface for a long period of time, it can be applied to the surface, left for a short period of time (e.g., 15-60 minutes), and then rinsed off with a high pressure fresh or sea water spray. This will minimize corrosion of the material to which it is applied, making it particularly effective for decontaminating aircraft and other equipment where corrosion is a concern. It will also minimize the time required for decontamination, which is particularly advantageous for military use (in the battlefield or at a fixed location).
Seawater may be effectively used as make-up water for the DF-200 formulation (part D). The following table shows the use of DF-200HF (2% PGD/3.50% H)2O2Per 4.0% bicarbonate) and seawater (. about.35,000 ppm total dissolved solids) kinetic test results:
table 7: DF-200HF formulation (2% PGD/3.50% H) containing seawater as make-up water (part D)2O2/4.0% bicarbonate).
Experiments with anthrax spore mimics (bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after 1 hour exposure to DF-200HF using sea water as make-up water.
Mustard and VX simulants were surface tested using DF-200 HF. For this test, 8mg of simulant was applied to a2 "diameter test piece made from CARC (chemical resistance paint). CARC is a material commonly used to coat military vehicles to protect them from chemical agents. After waiting for 1 hour, the test piece was placed in a horizontal position and washed with 1.0g DF-200HF (2% PGD/3.5% H)2O2/4.0% bicarbonate). After 60 minutes, the test piece was immersed in 25ml of acetonitrile for 15 minutes to extract unreacted simulant from the surface. The extraction solvent (acetonitrile) was then analyzed for unreacted simulant. The results (shown in Table 8) demonstrate more effective decontamination of the test pieces compared to DF-100A.
Table 8: results of the surface test of DF-200HF on CARC.
DF-200HF slurry (kit configuration)
For DF-200 formulations, insoluble bleach activators (e.g., TAED, NOBS, and N-acetylglucosamine) may be used in place of (water-soluble) propylene glycol diacetate. However, in this case, the formulation results in a slurry when mixed with water, rather than a true aqueous solution.
The present invention also provides a method of producing a reactive slurry (where a slurry is defined as comprising an aqueous mixture of insoluble, undissolved material) using a water-insoluble solid bleach activator (e.g., TAED). This embodiment, referred to as a "DF-200 HF slurry", is a variation of the DF-200HF formulation. Examples of 4-part kit configurations are shown below (illustrative amounts):
DF-200HF slurry (4-part kit)
Part A (foam concentrate)：
20gVariquat 80MC
10g of methyltrialkylammonium chloride 477
4g of 1-dodecanol
1g of Karl-type flocculant 8000 Polymer
5g of di (propylene glycol) methyl ether
7.5g of potassium bicarbonate
161g of water
Part B (solid component)：
50g of sodium percarbonate
50g of carbamide peroxide
Part C (Bleach activator)：
10g TAED (preferably sealed TAED, e.g. Warwick B637)
Part D (Water for Compensation)：
800g of water (which may be fresh or sea water supplied at the point of use)
The formulation described above will yield 1 liter of foam solution. The pH of the final formulation can be adjusted to about 9.6-9.8 for optimum performance. The following mixing steps may be used: mix part B to part D. Then, add part C and a to part B + D. Preferably within 8 hours.
For DF-200HF slurry (1% TAED/3% H)2O2/4% bicarbonate) performance for each chemical agent mimic is shown in table 9 below:
table 9: summary of the reaction rates of DF-200HF slurry formulations in kinetic experiments. It is noted that improved performance can be obtained by using higher concentrations of TAED (e.g., 2% TAED, rather than 1% TAED).
The above examples of different embodiments of DF-200 will typically be used in large scale operations where dedicated deployment devices and make-up water sources are readily available (e.g., for use by the military to clean "fixed sites" such as air force bases and seaports), or to minimize the volume of "prepackaged" water in order to minimize the weight of the formulation that needs to be shipped and stored.
DF-200 Rapid deployment configuration
The present invention also pertains to configurations that emphasize rapid deployment of the DF-200 formulation, and/or its deployment using a small deployment device (e.g., a hand-held device, a backpack-type device, or a cart-mounted device). For these applications, all water is "pre-packaged" into the formulation, so no additional water is needed in the field. For the first example of a 3-part kit configuration in the form of a DF-200HF quick-deployment, "DF-200 HF quick-deployment # 1", comprises (illustrative amounts):
DF-200HF Rapid expansion #1 (3-part kit)
Part A (liquid foam group)Minute)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
4g of 1-dodecanol
5g polyethylene oxide
8g of diethylene glycol monobutyl ether
5g of isobutanol
45g of potassium bicarbonate
About 19g potassium hydroxide (the pH of part A should be about 10.2)
933g of water
Part B (solid oxidizer component)：
97g Urea Hydrogen peroxide
Part C (liquid bleach activators)：
20g of propylene glycol diacetate
This configuration will produce 1 liter of foam solution. The pH of the final formulation can be adjusted to about 9.6-9.8 for optimum performance. The following mixing steps may be used: mix part B into part a. After the urea hydrogen peroxide has dissolved, part C is added to part a + B. Preferably within 8 hours. The performance of the DF-200HF rapid development for chemical agent mimics is shown in Table 10 below:
table 10: reaction rates from kinetic experiments with DF-200HF Rapid deployment #1 configuration.
Experiments with anthrax spore mimics (bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after 30 minutes of rapid deployment by exposure to DF-200 HF.
A diagrammatic example of a preferred mixing step for this first example of a DF-200HF fast deployment configuration is shown in fig. 2. Urea hydrogen peroxide is rapidly dissolved in water. Thus, the formulation can be prepared and deployed in a very short time at the scene of an accident involving chemical and biological warfare agents, making it ideal for use by civilian first responders (firefighters, hazardous materials units, police and other people who will first arrive at the CBW attack site) and/or military forces.
However, the particular bleach activator (propylene glycol diacetate) used in the present formulations is not stable in aqueous solutions where the pH is greater than about 9.9. It is therefore important to mix the correct components in the correct order. For example, if part C is mixed into part a before part B is added, DF-200HF may lose some activity because propylene glycol diacetate is exposed to a solution having a pH > 9.9. However, this is not true if part B is added to part a before part C, because part B addition to part a brings the pH of the part a + B mixture to a pH of less than about 9.9.
The solvent used in part a (foam solution) of the first example of DF-200HF quick develop #1 shown above, diethylene glycol monobutyl ether, is different from the solvent used in the DF-200HF formulation previously described (di (propylene glycol) methyl ether) because di (propylene glycol) methyl ether is not stable in the high pH environment required for the foam component (part a) in the quick develop apparatus. In addition, note that a short chain alcohol (i.e., isobutanol) has been added to the foam component (part A) in DF-200HF in the fast-open configuration # 1. While this low molecular weight alcohol may cause flammability problems in the highly concentrated DF-200HF configuration, it is not a problem in the less concentrated configurations described herein. The use of isobutanol also helps solubilize the 1-dodecanol in moiety a and improves the kinetics (chemical reactivity) of the formulation. In addition, the formulation preferably uses a different polymer, polyethylene oxide, than the polymer used in the other DF-200 formulations described earlier (i.e., the guar-based flocculant 8000). The alternative polymer is used because the guar 8000 is also unstable in the high pH environment of the liquid foam portion (part a) of the fast spreading formulation. Thus, a preferred formulation for DF-200HF Rapid deployment #1 comprises:
DF-200HF Rapid unfolding #1
1-4% (preferably 2%) Variquat80MC (cationic surfactant)
0.5-3% (preferably 1%) methyltrialkylammonium chloride 477 (cationic hydrotrope)
0.2-0.8% (preferably 0.4%) 1-dodecanol (aliphatic alcohol)
0.5-8% (preferably 0.5%) polyethylene glycol (polymer)
0.6-1.2% (preferably 0.8%) diethylene glycol monobutyl ether (solvent)
0-1% (preferably 0.5%) isobutanol (short chain alcohol)
0.1-10% (preferably 2-8%) bicarbonate (buffer and peroxide activator)
0.1-10% (preferably 1-4%) hydrogen peroxide (oxidant)
0.1-10% (preferably 1-4%) propylene glycol diacetate (bleach activator)
52-97% of water
The formulation can be adjusted to a pH of about 9.6-9.8 to achieve optimum performance, effective for decontamination of all agents of interest.
A second example of a 3-part kit configuration for the rapid deployment form of DF-200HF, "DF-200 HF Rapid deployment # 2", comprises (illustrative amounts):
DF-200HF Rapid expansion #2 (3-part kit)
Part A (liquid foam component)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
4g of 1-dodecanol
20g of polyethylene glycol 8000 Polymer
8g of diethylene glycol monobutyl ether
5g of isobutanol
50g of potassium bicarbonate
About 25g potassium hydroxide (the pH of part A should be about 10.2)
933g of water
Part B (solid oxidizer component)：
97g Urea Hydrogen peroxide
Part C (liquid bleach activators)：
20g of propylene glycol diacetate
In this second example, polyethylene glycol 8000 polymer replaced the polyethylene oxide polymer used in DF-200HF Rapid deployment # 1.
A third example of a 3-part kit configuration for the rapid deployment form of DF-200HF, "DF-200 HF Rapid deployment # 3", comprises (illustrative amounts):
pF-200HF Rapid development #3 (3-part kit)
Part A (liquid foam component)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
4g of 1-dodecanol
20g of polyethylene glycol 8000 Polymer
10g of hexanediol
45g Potassium carbonate
5g of potassium bicarbonate
700g of water
Part B (solid oxidizer component)：
83g of carbamide peroxide
Part C (liquid bleach activators)：
20g diacetin (i.e. diacetin)
In this third example, polyethylene glycol 8000 polymer replaced the polyethylene oxide polymer used in DF-200HF Rapid deployment #1 as the water soluble polymer. In addition, hexanediol replaces diethylene glycol monobutyl ether and isobutanol used as the solvent. Finally, diacetin (i.e., diacetin) replaces propylene glycol diacetate as a bleach activator. These changes to the third example were made to reduce or eliminate the use of short chain alcohols and/or high vapor pressure solvents to prevent possible problems associated with the very long term (months to years) shelf life of the liquid foam component (part a), particularly at high ambient storage temperatures due to evaporation of the most volatile components. Note that selecting a combination of 45 grams of potassium carbonate and 5 grams of potassium bicarbonate not only provides the correct amount of carbonate/bicarbonate, but also adjusts the pH appropriately. Alternatively, 50 grams of potassium bicarbonate (no potassium carbonate) can be used, and then the correct amount of potassium hydroxide (base) can be added to increase the pH to the desired value, as is well known in the art.
DF-200HF slurry Rapid deployment
The present invention also relates to a 2-part kit configuration for the rapid deployment embodiment of the DF-200HF slurry embodiment ("DF-200 HF slurry rapid deployment"), wherein TAED (or other solid peroxide activator) is used as the bleach activator. This example of a rapid deployment configuration also does not require the addition of additional water (in illustrative amounts) in the field:
DF-200 HF-slurry Rapid deployment (2-part kit)：
Part A (liquid foam component)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
4g of 1-dodecanol
5g polyethylene glycol
8g of diethylene glycol monobutyl ether
5
50g of potassium bicarbonate
28g potassium hydroxide (the pH of part A should be about 10.4)
953g of water
part B (solid oxidizing agent and bleach activator)：
97g Urea Hydrogen peroxide
30g TAED (preferably in a sealed form, e.g. Warwick International B637)
The formulation will yield 1 liter of foam solution. The pH of the final formulation can be adjusted to 9.6-9.8 for optimum performance. The formulation can be mixed using the following steps: mix part B into part a. Then, wait at least 1 minute before use to react TAED with hydrogen peroxide. Preferably within 8 hours. Note that TAED will not dissolve immediately in water, but it is useful that it will remain as solid particles for at least 15-20 minutes. Thus, a filter or screen may be required so that undissolved TAED particles will not damage or clog any pump or other components of the deployment apparatus. However, the formulation was ready for use about 1 minute after the addition of the TAED particles in part B to part a.
The use of TAED in sealed form in this configuration is effective for 2 reasons. First, the protective coating (which dissolves slowly in water) will protect the TAED so that it will not react with urea hydrogen peroxide during storage. Second, the coating will protect the TAED from the high pH conditions in part a until the carbamide peroxide dissolves and lowers the pH of the formulation to a value below about 9.9. With respect to protecting the activator from exposure to high pH solutions, TAED should be used in a similar manner as propylene glycol diacetate. If it is exposed to a solution having a pH greater than 9.9, the TAED will lose much of its effectiveness as a bleach activator. Thus, the use of TAED in a sealed form will minimize its immediate exposure to high pH conditions after mixing part B to part a. The performance of the DF-200HF slurry on chemical agent simulants with rapid deployment is given in Table 11 below.
Table 11: DF-200HF slurry rapidly developed the reaction rate of the formulation in the kinetic experiments.
Experiments with anthrax spore mimics (bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after 30 minutes of rapid deployment of DF-200HF slurry exposure.
A diagram illustrating an example of rapid deployment for field mixing of DF-200HF slurries is shown in fig. 3.
The above are but a few examples of rapid deployment configurations of DF-200 formulations. Other rapid deployment configurations are possible by utilizing the basic considerations described in this application, as will be appreciated by those of ordinary skill in the art.
The invention also relates to a process for preparing the foam component (part a) in a rapidly expanding configuration. The following are examples of such methods:
1. a suitable mass of water is placed in the mixing vessel.
2. The bicarbonate is added while the water in the mixing vessel is being stirred. Stirring until completely dissolved.
3. The polyethylene glycol polymer was slowly added to the mixing vessel while stirring rapidly. Care was taken to avoid caking. Stirring was minimum for about 30 minutes.
4. While stirring the foam solution in the mixing vessel, Variquat80MC was added. Stirring until complete mixing.
5. While stirring the foam solution in the mixing vessel, methyltrialkylammonium chloride 477 was added. Stirring until complete mixing.
6. Diethylene glycol monobutyl ether, isopropanol, and 1-dodecanol were mixed in separate vessels. The mixture was slowly added to the foam solution while stirring.
7. While stirring the foamy solution in the mixing vessel, solid KOH was slowly added until the pH reached the appropriate value.
Alternative DF-200 formulations
The present invention also relates to the following alternative DF-200 formulations:
1. alternative formulations that include propylene glycol to lower the freezing point of the solution;
2. alternative formulations utilizing sodium percarbonate as a solid source of hydrogen peroxide;
3. an alternative formulation comprising a corrosion inhibitor;
4. alternative formulations including glycerol as a viscosity building aid for operations such as surface cleaning;
5. utilizing an alternative formulation comprising an O-acetyl bleach activator provided in solid form; and
6. alternative formulations utilizing bleach activators comprising nitrile groups.
DF-200 containing propylene glycol
The following is a first example of a DF-200HF 2-part kit configuration comprising propylene glycol as the freezing point depressant, wherein all water is "prepackaged" in part a, including (illustrative amounts):
DF-200HF containing propylene glycolRapid deployment, first example (2-part kit)
Part A (liquid foam component)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
20g polyethylene glycol (MW 8000)
8g of diethylene glycol monobutyl ether
5g of isobutanol
4g 1-dodecanol
20g of propylene glycol diacetate
150g propylene glycol (freezing point depressant)
About 6g of 10% HCl solution (sufficient to produce a final pH of 2.5 in part A)
777g of water
Part B (solid additive)：
97g Urea Hydrogen peroxide
12g of potassium bicarbonate
38g Potassium carbonate (buffer, final pH adjustment)
The formulation will yield 1 liter of foam solution. The pH of the final formulation can be adjusted to about 9.6-9.8 for optimum performance. One of ordinary skill in the art will appreciate that the ratio of potassium carbonate to potassium bicarbonate used in part B can be adjusted to achieve the desired final pH of the formulation (preferably from about 9.6 to about 9.8). Thus, in this example, potassium carbonate was used as the base and source of carbonate/bicarbonate. To prepare the formulation, part B was mixed into part a. Preferably within 8 hours. The performance of this first example of DF-200HF containing propylene glycol for the chemical reagent simulant is shown in Table 12.
Table 12: reaction rates from kinetic experiments with DF-200HF containing propylene glycol (first example).
Experiments with anthrax spore mimics (bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after 30 minutes exposure to DF-200HF containing propylene glycol (first example).
When all the water is "pre-packaged" in part a, since it consists of only 2 parts, the formulation mixing can be done for use in a very short time. It can therefore be deployed very quickly at the scene of an accident involving chemical and biological warfare agents. This configuration is ideal for use by folk first responders (firefighters, hazardous materials units, police stations, and others who will arrive first at the CBW attack site). However, it is more portable than other configurations that add water in the field.
This configuration also incorporates the bleach activator, propylene glycol diacetate, into the foam component part a (rather than storing it as a separate third component). This is possible because the pH of the foam component is less than 3. Propylene glycol diacetate will hydrolyze in solutions at pH greater than 3 but is hydrolytically stable in solutions at pH less than 3. This configuration also uses a polyethylene glycol polymer (PEG8000) for viscosity enhancement. The polymers are used in many cosmetic products and are very soluble and stable in water. In addition, because it has no tendency to cake, it is more easily mixed into solution than the guar-type flocculant 8000 or high molecular weight polyethylene oxide.
The formulation includes propylene glycol as a freezing point depressant. Propylene glycol is considered an environmentally friendly antifreeze. In this case, the concentration is about 15% by weight, which lowers the freezing point of part a to about-20 ℃. This configuration has also been tested with good results using propylene glycol concentrations up to 40% by weight.
An alternative to the first example of propylene glycol-containing DF-200HF shown above is to use sodium percarbonate as the source of bicarbonate and part of the peroxide in part B instead of urea hydrogen peroxide. This replacement is useful because sodium percarbonate is much cheaper than urea hydrogen peroxide. This second example of DF-200HF containing propylene glycol is shown below (illustrative amounts):
DF-200HF Rapid unfolding with propylene glycol, second example (2-part kit)
Part A (liquid foam component)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
20g polyethylene glycol (MW 8000)
8g of diethylene glycol monobutyl ether
5g of isobutanol
4g of 1-dodecanol
20g of propylene glycol diacetate
150g propylene glycol (freezing point depressant)
About 6g of 10% HCl solution (sufficient to produce a final pH of 2.5 in part A)
777g of water
Part B (solid additive)：
90g of sodium percarbonate
15g citric acid (buffer, final pH adjustment)
The formulation will yield 1 liter of foam solution. The pH of the final formulation can be adjusted to about 9.6-9.8 for optimum performance. The following mixing steps may be used: mix part B into part a. Preferably within 8 hours. Alternatively, sodium bisulfate (common combination conditioning chemicals), or other acids can be used in place of citric acid to adjust the pH. The performance of this second example of DF-200HF containing propylene glycol (using sodium percarbonate) against chemical agent mimics is shown in Table 13.
Table 13: reaction rates from kinetic experiments with a second example of DF-200HF containing propylene glycol (using sodium percarbonate).
Generally, sodium percarbonate dissolves much more slowly than urea hydrogen peroxide after it has been added to part a. However, to increase the solubilization rate, the sodium percarbonate can be ground to about 100 mesh size to suit the use of this configuration. When ground sodium percarbonate is used, the time to dissolve the sodium percarbonate is reduced from about 30 minutes to about 2 minutes.
DF-200 containing sodium-buffering agent
Corrosion inhibitors may be added to DF-200 formulations to reduce their corrosiveness. A preferred corrosion inhibitor for DF-200 formulations is N, N-dimethylethanolamine. However, other corrosion inhibitors such as triethanolamine, mixtures of ethanolamine salts of C9, C10, and C12 diacids, dicyclohexylamine nitrite, and N, N-dibenzylamine may be used. Corrosion inhibitors incorporating DF-200 formulations can be used for multiple purposes:
1. a corrosion inhibitor, a metal oxide,
a pH buffering agent for the pH of the solution,
3. a solvent which holds 1-dodecanol in solution, and
4. solubilizing co-solvents for insoluble chemicals such as sarin or mustard.
Examples of 3-part kit configurations for DF-200HF containing corrosion inhibitors include (illustrative amounts):
DF-200HF quick expansion containing corrosion inhibitor (3-part kit)
Part A (liquid foam component)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
4g of 1-dodecanol
5g polyethylene glycol
10g N, N-dimethylethanolamine (corrosion inhibitor)
50g of potassium bicarbonate
About 18g of potassium hydroxide (sufficient to produce a final pH of 10.2 in part A)
936g of water
Part B (solid oxidizer component)：
97g Urea Hydrogen peroxide
Part C (liquid bleach activators)：
20g of propylene glycol diacetate
The formulation will yield 1 liter of foam solution. The pH of the final formulation can be adjusted to about 9.6-9.8 for optimum performance. The following mixing steps may be used: mix part B into part a. Then, after the urea hydrogen peroxide has dissolved, add part C to parts a + B. Preferably within 8 hours. The performance of DF-200HF with corrosion inhibitor against chemical agent simulants is given in Table 14.
Table 14: reaction rate in kinetic experiments with DF-200HF containing corrosion inhibitor.
Experiments with anthrax spore mimics (bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after 60 minutes of exposure to DF-200HF containing a corrosion inhibitor. The addition of the corrosion inhibitor had a deleterious effect on the performance of DF-200 against chemical agents, but had no measured effect on the performance of DF-200HF against biological agents. Similar results were obtained when the alternative corrosion inhibitor, 1% triethanolamine, was used.
DF-200 containing Glycerol
In another embodiment of the DF-200 formulation, glycerin may be used as a viscosity building aid in place of the guar-based flocculant 8000, polyethylene oxide, or polyethylene glycol. Glycerol is a common ingredient in cosmetics, where it is used as a viscosity building aid as well as a solvent, humectant and emollient. Thus, the use of glycerol in DF-200 formulations can serve multiple purposes:
1. a viscosity-enhancing auxiliary agent,
2. humectants (i.e. substances that moisturize the skin),
3. a solvent which holds 1-dodecanol in solution, and
4. solubilizing co-solvents for insoluble chemicals such as sarin or mustard.
Examples of DF-200HF 3-part kit configurations containing glycerol include (illustrative amounts):
DF-200HF Rapid development with Glycerol (3-part kit)
Part A (liquid foam component)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
4g of 1-dodecanol
40g Glycerol (viscosity builder)
40g of potassium bicarbonate
About 17g potassium hydroxide (sufficient to produce a final pH of 10.2 in part A)
906g of water
Part B (solid oxidizer component)：
97g Urea Hydrogen peroxide
Part C (liquid bleach activators)：
20g of propylene glycol diacetate
The formulation will yield 1 liter of foam solution. The pH of the final formulation can be adjusted to about 9.6-9.8 for optimum performance. The following mixing steps may be used: mix part B into part a. Then, after urea hydrogen peroxide has dissolved, add part C to part +/B. Preferably within 8 hours. The performance of DF-200HF containing glycerol for the chemical reagent simulants is given in Table 15.
Table 15: reaction rate in kinetic experiments with DF-200HF containing Glycerol.
Experiments with anthrax spore mimics (bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after 30 minutes exposure to DF-200HF containing glycerol.
Because glycerin will act as a humectant, the formulation can be used for direct application to humans. The formulation can be used, for example, as a spray or shower by removing foaming components (such as 1-dodecanol and methyltrialkylammonium chloride 477), and by reducing the concentration of peroxide. However, glycerol is used with the disadvantage that it is a solid at relatively high temperatures (below about 10 ℃). Therefore, it will be preferably used under controlled temperature conditions (i.e., heating temperature conditions).
Propylene glycol diacetate, a bleach activator used in many of the previously described DF-200 configurations, is not currently available in solid form. However, other bleach activators are available in solid form.
DF-200 containing acetylcholine chloride
Solid O-acetyl bleach activators (e.g. acetylcholine chloride, which is often used in eye drops) may be used in the DF-200 formulations in place of (liquid) propylene glycol diacetate. The chemical structure of this O-acetyl bleach activator is shown below. It can be seen that this molecule contains an O-acetyl group which activates the peroxide, and it is a quaternary compound, very suitable for use with DF-200 formulations. Acetylcholine chloride is also soluble and very hygroscopic in water.
An example of a 2-part kit configuration for DF-200HF using acetylcholine chloride comprises (illustrative amounts):
DF-200HF Rapid deployment Using acetylcholine chloride (2-part kit)
Part A (liquid foam component)：
20g Variquat 80MC
10g of methyltrialkylammonium chloride 477
30g polyethylene glycol (MW 8000)
8g of diethylene glycol monobutyl ether
5g of isobutanol
4g of 1-dodecanol
150g propylene glycol
50g of potassium bicarbonate
About 17g potassium hydroxide (sufficient to produce a final pH of 10.2 in part A)
803g of water
Part B (solid additive)：
97g Urea Hydrogen peroxide
25g of acetylcholine chloride (solid bleach activator)
The formulation will yield 1 liter of foam solution. The pH of the final formulation can be adjusted to about 9.6-9.8 for optimum performance. To use the formulation, part B is mixed into part a. Preferably within 8 hours. The performance of DF-200HF using acetylcholine chloride for chemical reagent mimics is shown in Table 16.
Table 16: reaction rates from kinetic experiments with DF-200HF using acetylcholine chloride as an activator.
Experiments with anthrax spore mimics (Bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after 30 minutes exposure to DF-200HF using acetylcholine chloride.
Other 2O-acetyl bleach activators, monoacetin (glycerol monoacetate) and diacetin (glycerol diacetate), have been tested for their effectiveness in DF-200 formulations. Both compounds have also proven to be extremely effective bleach activators. These compounds are water soluble liquids.
Experiments have shown that the peroxide in DF-200 formulations is also effectively activated by nitrile containing compounds such as 4-cyanobenzoic acid (which is water soluble) at concentrations of, for example, 2% to neutralize chemical and biological agent mimics.
DF-200 Using Peracetic acid
Peracetic acid was used as the oxidizing agent in DF-200 to perform the experiment instead of hydrogen peroxide. The following formulations were used:
2% Variquat80MC (cationic surfactant)
2% peracetic acid (oxidant)
5% Potassium bicarbonate (buffer and activator)
91% water
The formulations were adjusted to pH 9.8 with solid KOH and tested against the simulants mustard, VX and anthrax spores. The performance of this formulation against chemical reagent mimics is shown in table 17.
Table 17: reaction rate of kinetic experiments with DF-200 containing 2% peracetic acid.
Experiments with anthrax spore mimics (bacillus subtilis spores) demonstrated 99.9999% (7-log) kill after exposure to DF-20030 minutes with 2% peracetic acid.
The experiment was also performed for DF-200 using a higher concentration of peracetic acid (3.5%) in the following formulations:
2% Variquat80MC (cationic surfactant)
3.5% peracetic acid (oxidant)
5% Potassium bicarbonate (buffer and activator)
89.5 percent of water
The formulations were adjusted to pH 9.8 using solid KOH and tested against the simulants mustard, VX and anthrax spores. The performance of this formulation against chemical reagent mimics is shown in table 18.
Table 18: reaction rate of kinetic experiments with DF-200 containing 3.5% peracetic acid.
The results show that the use of peracetic acid as an alternative oxidizing agent is effective for chemical agent mimics, but not as effective as DF-200 formulations using activated hydrogen peroxide (i.e., a combination of hydrogen peroxide, bicarbonate, and propylene glycol diacetate) as the oxidizing agent. However, DF-200 formulations containing 2-3.5% peracetic acid were very effective at killing spores. However, because peracetic acid is not currently available in a safe, convenient solid form, and has a relatively short shelf life in liquid form, the use of this oxidizing agent is less attractive than hydrogen peroxide.
Tests were also conducted to determine the minimum component required to kill spores in DF-200 formulations using peracetic acid as the oxidizing agent. These results show that only 3 components, peracetic acid, bicarbonate, and cationic surfactant, are necessary to achieve high rates of spore kill.
Living agent assay Using DF-200HF
Live reagent tests were performed on 3 chemical reagents, 1, 2, 2-trimethylpropyl methylphosphonyl fluoride ("GD"), VX, and mustard ("HD"), and 2 biological reagents (anthrax spores and Yersinia pestis). The results of the kinetic testing of DF-200HF (using the 3-part configuration) against the chemical agents are shown in Table 19.
Table 19: reaction rate in dynamic experiments of DF-200HF on chemical reagents.
Following exposure of GD to DF-200HF, methylphosphonic acid (MPA) and pinacolmethylphosphonic acid (MPA) were identified as by-products. Following exposure of VX to DF-200HF, ethylmethylphosphonic acid (EMPA) and MPA were identified as by-products. This suggests that VX destruction follows a more desirable pathway to the phosphonic acid, rather than to EA2192 (a toxic by-product that may also be produced during VX degradation). Finally, after exposure of HD to DF-200HF, the HD initial degradation products contain a mixture of sulfoxide and sulfone byproducts, each of which almost completely disappears later followed by 60 minutes.
The results of the experiments on anthrax spores are shown in tables 20 and 21, and the results of the experiments on yersinia pestis (i.e. plague bacteria) are shown in table 22(NG means "no growth"). The limit of detection for these tests was 10 CFU/ml. Note that the "error bar" in the "% reduction" column takes this detection limit into account.
Table 20: the rate of killing of the spores of Bacillus anthracis AMES-RIID in DF-200HF solution.
Table 21: rate of killing of Bacillus anthracis ANR-1 spores in DF-200HF solution.
| Bacillus anthracis ANR-1 | Average CFU/ml | Log reduction | % reduction |
| Control | 6.42E+07 | 0 | 0/00 |
| Bacillus anthracis ANR-1 | Average CFU/ml | Log reduction | % reduction |
| 15 minutes of contact | NG | 7 | 100±.00004 |
| 30 minutes of contact | NG | 7 | 100±.00004 |
| 60 minutes of contact | NG | 7 | 100±.00004 |
Table 22: rate of Yersinia pestis cell killing in DF-200HF solution.
After experiments that confirmed that DF-200HF had actually killed spores rather than only inhibited their growth, the dishes used for cell growth in each of these experiments were kept for 21 days. No growth was observed on any dish after the 21 day period.
Toxic industrial chemical assay using DF-200HF
Several Toxic Industrial Chemicals (TIC) were also tested against DF-200 HF. A summary of the TICs tested to date and the results of those tests are shown in table 23. Note that the results for malathion, butyl isocyanate, sodium cyanide, and carbon disulfide were obtained by analyzing the unreacted chemicals in the foam solution, while the results for phosgene were obtained by analyzing the chemicals in the headspace above the foam solution. These results demonstrate effective neutralization of these toxic industrial chemicals.
Table 23: summary of Toxic Industrial Chemical (TIC) neutralization experiments using DF-200 HF.
The previous examples may be repeated with equal success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the previous examples.
While the invention has been described in detail with particular reference to these preferred embodiments, other embodiments can achieve the same results. Variations and modifications of the present invention will be obvious to those skilled in the art, and it is intended to cover in the appended claims all such modifications and equivalents. All of the above cited references, applications, patents and publications are incorporated herein by reference in their entirety.
Claims (34)
1. A formulation for neutralizing at least one chemical, biological, and industrial toxant, the formulation comprising:
at least two solubilizing compounds, wherein at least one solubilizing compound is a cationic surfactant selected from quaternary ammonium salts and at least one solubilizing compound is a cationic hydrotrope;
at least one reactive compound, wherein the at least one reactive compound is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, hydroperoxycarbonates, peracetic acid, sodium perborate, sodium peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and
at least one water soluble bleach activator selected from the group consisting of ethylene glycol diacetate, propylene glycol monomethyl ether acetate, methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate, and propylene glycol diacetate, and combinations thereof;
wherein the at least two solubilizing compounds, the at least one reactive compound, and the at least one water-soluble bleach activator, when mixed with water and exposed to the at least one chemical, biological, and industrial toxant, neutralize the at least one chemical, biological, and industrial toxant.
2. The formulation according to claim 1, wherein the cationic surfactant comprises a quaternary ammonium salt.
3. The formulation according to claim 2, wherein said quaternary ammonium salt is selected from the group consisting of cetyltrimethylammonium bromide, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyldimethylbenzylammonium salts, tetrabutylammonium bromide, and mixtures of benzyl (C12-C16) alkyldimethylammonium chlorides, and combinations thereof.
4. The formulation according to claim 1, which additionally comprises a water-soluble polymer.
5. A formulation according to claim 4, wherein the water-soluble polymer is selected from polyvinyl alcohol, guar gum, (cationic or non-ionic) polydiallyldimethylammonium chloride, polyacrylamide, poly (ethylene oxide), polyethylene glycol 8000(PEG8000), or guar gum type flocculating agent 8000TM(guar 2-hydroxypropyl ether), and combinations thereof.
6. The formulation according to claim 1, which additionally comprises an aliphatic alcohol having 8 to 20 carbon atoms per molecule.
7. The formulation according to claim 1, which additionally comprises a solvent.
8. The formulation according to claim 7 wherein the solvent comprises one of di (propylene glycol) methyl ether and diethylene glycol monobutyl ether and combinations thereof.
9. The formulation according to claim 1, which additionally comprises a carbonate.
10. The formulation according to claim 9 wherein the carbonate salt is selected from the group consisting of potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, lithium bicarbonate, ammonium carbonate, and potassium carbonate, and combinations thereof.
11. The formulation according to claim 1 wherein said at least one bleach activator is propylene glycol diacetate.
12. The formulation according to claim 1, wherein the formulation has a pH of 9.6-9.8 when mixed with water.
13. The formulation according to claim 1, which is packaged in a kit configuration.
14. The formulation according to claim 13, wherein the kit formulation comprises:
a premix component comprising the at least 2 solubilizing agents;
a first component comprising the at least one bleach activator; and
a second component comprising the at least one reactive compound.
15. The formulation according to claim 14, which additionally comprises water and a base.
16. The formulation according to claim 14 wherein said premix components additionally comprise a water soluble polymer.
17. The formulation according to claim 14 wherein said at least one bleach activator is selected from the group consisting of propylene glycol diacetate, diacetin, and TAED, and combinations thereof.
18. The formulation according to claim 14 wherein said premixed component additionally comprises an aliphatic alcohol containing from 8 to 20 carbon atoms per molecule.
19. The formulation according to claim 14 wherein said at least one reactive compound comprises urea hydrogen peroxide and wherein said second component comprising said at least one reactive compound additionally comprises sodium percarbonate.
20. The formulation according to claim 14 wherein said premixed component additionally comprises a short chain alcohol.
21. The formulation according to claim 13, wherein the kit formulation comprises:
a first premix component comprising the at least 2 solubilizing agents and water; and
a second pre-mix component comprising the at least one bleach activator and the at least one reactive compound, wherein the at least one bleach activator is in solid form.
22. The formulation according to claim 21 wherein said first premix component additionally comprises an acid.
23. The formulation according to claim 13, wherein the kit formulation comprises:
a premix component comprising the at least two solubilizers and the at least one bleach activator; and
a component comprising the at least one reactive compound.
24. The formulation according to claim 23 wherein said premix components additionally comprise water and an acid.
25. The formulation according to claim 23, wherein said component comprising said at least one reactive compound comprises sodium percarbonate and additionally comprises an acid.
26. The formulation according to claim 23 wherein said at least one reactive compound comprises urea hydrogen peroxide and wherein said component comprising said at least one reactive compound additionally comprises a mixture of potassium carbonate and potassium bicarbonate.
27. A formulation for neutralizing at least one chemical, biological, and industrial toxant, the formulation comprising:
at least one cationic surfactant;
at least one carbonate salt selected from the group consisting of potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, lithium bicarbonate, ammonium carbonate, and potassium carbonate, and combinations thereof;
at least one reactive compound, wherein the at least one reactive compound is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, hydroperoxycarbonates, peracetic acid, sodium perborate, sodium peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate;
at least one water soluble bleach activator selected from the group consisting of ethylene glycol diacetate, propylene glycol monomethyl ether acetate, methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate, and propylene glycol diacetate, and combinations thereof; and
wherein the at least one surfactant, the at least one reactive compound, and the at least one water-soluble bleach activator neutralize the at least one chemical, biological, and industrial toxant when mixed with water and exposed to the at least one chemical, biological, and industrial toxant.
28. The formulation according to claim 27, wherein said cationic surfactant comprises a quaternary ammonium salt.
29. The formulation according to claim 28, wherein said quaternary ammonium salt comprises benzalkonium chloride.
30. The formulation according to claim 27, wherein the formulation has a pH of 9.6-9.8 when mixed with water.
31. The formulation according to claim 27 consisting essentially of said at least one cationic surfactant, said at least one carbonate salt, said at least one reactive compound, and said at least one water-soluble bleach activator.
32. A formulation according to claim 31, consisting essentially of:
1-10% benzalkonium chloride;
1-8% propylene glycol diacetate;
1-16% hydrogen peroxide;
2-8% potassium bicarbonate; and
the balance being water.
33. A formulation for neutralizing at least one chemical, biological, and industrial toxant, the formulation comprising:
at least two solubilizing compounds, wherein at least one solubilizing compound is a cationic surfactant selected from quaternary ammonium salts and at least one solubilizing compound is a cationic hydrotrope;
at least one reactive compound, wherein the at least one reactive compound is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, hydroperoxycarbonates, peracetic acid, sodium perborate, sodium peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and
at least one water-soluble bleach activator selected from the group consisting of acetylcholine chloride, monoacetin (glycerol monoacetate), diacetin (glycerol diacetate), 4-cyanobenzoic acid, and triacetin (glycerol triacetate), and combinations thereof;
wherein the at least two solubilizing compounds, the at least one reactive compound, and the at least one water-soluble bleach activator, when mixed with water and exposed to the at least one chemical, biological, and industrial toxant, neutralize the at least one chemical, biological, and industrial toxant.
34. A formulation for neutralizing at least one chemical, biological, and industrial toxant, the formulation comprising:
at least one cationic surfactant selected from quaternary ammonium salts;
at least one carbonate salt selected from the group consisting of potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, lithium bicarbonate, ammonium carbonate, and potassium carbonate, and combinations thereof;
at least one reactive compound, wherein the at least one reactive compound is selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, hydroperoxycarbonates, peracetic acid, sodium perborate, sodium peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate;
at least one water-soluble bleach activator selected from the group consisting of acetylcholine chloride, monoacetin (glycerol monoacetate), diacetin (glycerol diacetate), 4-cyanobenzoic acid, and triacetin (glycerol triacetate), and combinations thereof; and
wherein the at least one surfactant, the at least one reactive compound, and the at least one water-soluble bleach activator neutralize the at least one chemical, biological, and industrial toxant when mixed with water and exposed to the at least one chemical, biological, and industrial toxant.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US32650801P | 2001-10-01 | 2001-10-01 | |
| US60/326,508 | 2001-10-01 | ||
| US33427101P | 2001-11-30 | 2001-11-30 | |
| US60/334,271 | 2001-11-30 | ||
| US38710402P | 2002-06-07 | 2002-06-07 | |
| US60/387,104 | 2002-06-07 | ||
| PCT/US2002/029886 WO2003028429A2 (en) | 2001-10-01 | 2002-09-20 | Enhanced formulations for neutralization of chemical, biological and industrial toxants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1073618A1 HK1073618A1 (en) | 2005-10-14 |
| HK1073618B true HK1073618B (en) | 2010-12-17 |
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