EP1434625B1 - Formulations ameliorees permettant de neutraliser des substances toxiques chimiques, biologiques et industrielles - Google Patents

Formulations ameliorees permettant de neutraliser des substances toxiques chimiques, biologiques et industrielles Download PDF

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EP1434625B1
EP1434625B1 EP02775899.4A EP02775899A EP1434625B1 EP 1434625 B1 EP1434625 B1 EP 1434625B1 EP 02775899 A EP02775899 A EP 02775899A EP 1434625 B1 EP1434625 B1 EP 1434625B1
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water
formulation
reactive compound
propylene glycol
hydrogen peroxide
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EP1434625A2 (fr
EP1434625A4 (fr
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Mark D. Tucker
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National Technology and Engineering Solutions of Sandia LLC
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National Technology and Engineering Solutions of Sandia LLC
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors

Definitions

  • the present invention relates to formulations for neutralization of chemical, biological and industrial toxants.
  • the present invention is directed to materials and methods for neutralization of toxic chemical, biological and industrial compounds or agents, especially chemical and biological weapons agents, and methods of making same.
  • the present invention is directed to materials containing solubilizing compounds, reactive compounds and bleaching activators that can be delivered as foams, sprays, liquids, fogs and aerosols to enhance the rate of reactions leading to neutralization of chemical compounds, and other additives which serve to kill or attenuate certain biological compounds or agents.
  • Terrorist threats potentially involving 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 paramount concern both to national defense as well as to state and local law enforcement.
  • the chemical agents sarin, soman, and tabun (G-agents) are all examples of phosphorus-containing compounds which, when altered chemically, can lose their toxicity.
  • Mustard which is an example of the H-agents
  • VX which is an example of the V-agents
  • BW agents include botulinum toxin, anthrax and other spore-forming bacteria, vegetative bacteria, including plague and various viruses can also be deactivated chemically.
  • a CW or biological warfare (“BW”) attack can involve either local placement or wide dispersal of the agent or agents so as to affect a population of human individuals. Because of the flexibility with which CW and BW (“CBW”) agents can be deployed, respondents might encounter the agents in a variety of physical states including bulk, aerosol and vapors.
  • BW biological warfare
  • An effective, rapid, and safe (non-toxic and non-corrosive) decontamination technology is required for the restoration of civilian facilities in the event of a domestic terrorist attack.
  • this technology should be applicable to a variety of scenarios such as the decontamination of open, semi-enclosed, and enclosed facilities as well as sensitive equipment.
  • Examples of types of facilities where the decontamination formulation may be utilized include a stadium (open), an underground subway station (semi-enclosed), and an airport terminal or office building (enclosed).
  • a foaming version is useful for extending the contact time of the formulation on vertical surface.
  • Decontamination of chemical compounds have focused primarily on chemical warfare agents, particularly on the nerve agents (such as G agents and V agents) and on the blistering agents (such as mustard gas, or simply, mustard). Reactions involved in 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 of all microorganisms to kill. Additional background is discussed in U.S. Patent Applications Serial Nos. 09/607,586 and 09/952,940 .
  • This formulation can be adjusted to a pH value of 8 for optimal decontamination of Mustard and Anthrax spores; and can be to a pH value of 10 for optimal decontamination of VX.
  • Decontamination of chemical agents is generally effective anywhere between pH 8 and 10. Also, it can be adjusted to a pH of 9.2 for less than optimal decontamination of all agents.
  • the hydrogen peroxide and bicarbonate salt react to produce a highly reactive negatively charged nucleophillic species, hydroperoxycarbonate (HCO4), which is a strong oxidant.
  • HCO4 hydroperoxycarbonate
  • Other negatively-charged nucleophiles are formed by the use of hydrogen peroxide, including: hydroxyl ions (OH) and hydroperoxide ions (OOH).
  • OH hydroxyl ions
  • OOH hydroperoxide ions
  • the present invention presents enhanced decontamination formulations (generically designated"DF-200") that include bleaching activators, which leads to faster reaction kinetics, improved performance, and the elimination of the need for pH adjustment.
  • bleaching activators are commonly used in (anionic) laundry detergents
  • the present invention can employ them with cationic surfactants, and where good solubility in water of the activator is useful for achieving quick reaction times.
  • a desirable bleaching activator for use in the present invention is preferably water-soluble, non-toxic, non-flammable, and low-cost.
  • Glucose pentaacetate is an 0-acetyl peroxide activator that has been used as an activation agent in a sterilizing composition comprising a cationic surface-active agent and inorganic peroxide (See Japanese Laid-Open Patent Publication No. 62-155203 , entitled"Sterilizing Composition for Cattle Shed” (1987)).
  • Glucose pentaacetate is a solid at room temperature (i. e. , melting point 110 degrees C), 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 glucose pentaacetate concentration of about 2%, it takes several hours to dissolve. This makes its use less than desirable for rapid deployment configurations.
  • FR 2 766 724 discloses a decontaminating solution comprising an organic or mineral peroxide, at least one surfactant comprising an amine oxide and an alkaline buffer.
  • US 3 901 819 discloses a composition for activating an inorganic peroxide bleaching agent comprising an acetic ester of a monosaccharide, a disaccharide, a sugar alcohol, an internal anhydride of a sugar alcohol, or erythritol, and mixtures thereof, said ester having at least 2 ester groups on the adjacent carbon atom and an acetic ester of a polyhydric alcohol.
  • US 4 850 729 relates to decontaminating composition and a delivery system therefor.
  • the decontaminating composition is prepared by combining "per-salt", an activator for hxdrogen peroxide, both of which are in a dry form, and an aqueous solution comprised of a nonvolatile alcohol and a surface active agent.
  • the decontaminating composition and delivery system comprise a dispenser containing, in separate compartments, the various components as aforesaid which are thoroughly mixed prior to being dispensed onto the surface to be treated.
  • the present invention is of a formulation for use in neutralization of at least one toxant comprising at least one solubilizing compound, selected from the group consisting of a cationic hydrotrope and a fatty alcohol comprising from 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, hydroperoxycarbonate, peracetic acid, sodium perborate, sodium peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and at least one water-soluble bleaching activator selected from the group consisting of 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 one solubilizing compound, the at least one reactive compound, and the at least one bleaching activator, when mixed with water and exposed to the at least one toxant,
  • the formulation for use in neutralization of at least one toxant comprises : 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 peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and at least one water-soluble bleaching activator selected form the group consisting of propylene glycol monomethyl ether acetate, methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate, and propylene glycol diacetate and combinations thereof; wherein at least two solubilizing compounds, the at least one reactive compound and the at least one water-soluble bleaching activator, when mixed with water and exposed to the at least one toxant
  • the cationic surfactant comprises a quaternary ammonium salt, most preferably cetyltrimethyl ammonium bromide, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyidimethylbenzylammonium salt, tetrabutyl ammonium bromide, or WITCO VARIQUAT 80MC, or a combination thereof.
  • a quaternary ammonium salt most preferably cetyltrimethyl ammonium bromide, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyidimethylbenzylammonium salt, tetrabutyl ammonium bromide, or WITCO VARIQUAT 80MC, or a combination thereof.
  • the formulation may further comprise water-soluble polymer, preferably polyvinyl alcohol, guar gum, (cationic or non-ionic) polydiallyl dimethyl ammonium chloride, polyacrylamide, poly (ethylene oxide), glycerol, polyethylene glycol 8000 (PEG 8000), or JAGUAR 8000TM (Guar Gum 2-hydroxypropyl ether), or a combination thereof.
  • water-soluble polymer preferably polyvinyl alcohol, guar gum, (cationic or non-ionic) polydiallyl dimethyl ammonium chloride, polyacrylamide, poly (ethylene oxide), glycerol, polyethylene glycol 8000 (PEG 8000), or JAGUAR 8000TM (Guar Gum 2-hydroxypropyl ether), or a combination thereof.
  • the formulation may also further comprise a fatty alcohol comprising from 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, ammonium hydrogen bicarbonate, lithium bicarbonate, ammonium carbonate, or potassium carbonate, or a combination thereof).
  • a solvent preferably Di (propylene glycol) methyl ether or diethylene glycol monobutyl ether or a combination thereof
  • a carbonate salt preferably potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, ammonium hydrogen bicarbonate, lithium bicarbonate, ammonium carbonate, or potassium carbonate, or a combination thereof.
  • the bleaching activator is water-soluble, 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 a combination thereof. glucosamine, or a combination thereof.
  • the formulation when mixed with water, preferably has a pH value between about 9.6 and about 9.8.
  • One embodiment of the invention consists essentially of 110% Benzalkonium Chloride, 1-8% Propylene Glycol Diacetate; 1-16% Hydrogen Peroxide; and 28% Potassium Bicarbonate.
  • the invention is also of a formulation for use in neutralization of at least one toxant, comprising: at least one cationic surfactant and at least one 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 peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; at least one water-soluble bleaching 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 at least one carbonate salt not one of the at least one reactive compounds; wherein the at least one surfactant, the at least one reactive compound, the at least one bleaching activator, and the at least one carbonate salt, when mixed with water and exposed to the
  • the formulation when mixed with water, has a pH value between about 9.6 and about 9.8 and the cationic surfactant comprises a quaternary ammonium salt, most preferably benzalkonium chloride.
  • the at least one carbonate salt is potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, ammonium hydrogen bicarbonate, lithium bicarbonate, ammonium carbonate, or potassium carbonate, or a combination thereof.
  • One embodiment consists substantially of the at least one cationic surfactant, the at least one reactive compound, the at least one bleaching activator, and the at least one carbonate salt.
  • the bleaching activator is 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 a combination thereof.
  • 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 (
  • the invention is further of a formulation for use in neutralization of at least one toxant, comprising: at least one cationic surfactant and at least one 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 peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and at least one water-soluble bleaching 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 one surfactant, the at least one reactive compound, and the at least one watersoluble bleaching activator, when mixed with water and exposed to the at least one toxant, neutralizes the at least one toxant.
  • the at least one water-soluble bleaching 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 further comprises at least one carbonate salt, selected from the group consisting of potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, ammonium hydrogen bicarbonate, lithium bicarbonate, ammonium carbonate, or potassium carbonate, or a combination thereof.
  • the formulation when mixed with water, preferably has a pH value between about 9.6 and about 9.8.
  • One embodiment consists substantially of the at least one cationic surfactant, the at least one reactive compound, and the at least one water-soluble bleaching activator.
  • kits comprises: a premixed component comprising at least two solubilizing agents; a first component comprising at least one water-soluble bleaching activator; and a second component comprising at least one reactive compound.
  • the first embodiment may further comprise water and a base
  • the premixed component may additionally comprise a water-soluble polymer
  • the at least one bleaching activator is preferably propylene glycol diacetate, glycerol diacetate, and/or TAED
  • the premixed component may additionally comprise a fatty alcohol comprising from 8 to 20 carbon atoms per molecule
  • the at least one reactive compound may be urea hydrogen peroxide with the second component comprising the at least one reactive compound additionally comprising sodium percarbonate
  • the premixed component may additionally comprise a short-chained alcohol.
  • a second embodiment comprises: a first premixed component comprising at least two solubilizing agents and water; and a second premixed component comprising at least one bleaching activator and the at least one reactive compound, wherein the at least one bleaching activator is in solid form.
  • the first premixed component preferably additionally comprises an acid
  • the at least one bleaching activator preferably comprises acetycholine chloride
  • the at least one reactive compound comprises urea hydrogen peroxide and the at least one bleaching activator comprises TAED
  • the at least one bleaching activator is encapsulated to prevent premature reaction with the at least one reactive compound.
  • a third embodiment comprises: a premixed component comprising at least two solubilizing agents and at least one bleaching activator; and a component comprising at least one reactive compound.
  • the premixed component may additionally comprise water and an acid
  • the component comprising the at least one reactive compound may comprise sodium percarbonate and additionally an acid
  • the at least one reactive compound may comprise urea hydrogen peroxide with the component comprising the at least one reactive compound additionally comprising a mixture of potassium carbonate and potassium bicarbonate.
  • the invention is further of a formulation for use in neutralization of at least one toxant, 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, hydroperoxycarbonate, peracetic acid, sodium perborate, sodium peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and at least one water-soluble bleaching activator selected from the group consisting of O-acetyl, N-acetyl, and nitrile group bleaching activators; wherein the at least one surfactant, the at least one reactive compound, and the at least one water-soluble bleaching activator, when mixed with water and exposed to the at least one toxant, neutralizes the at least one toxant.
  • the at least one water-soluble bleaching 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 further comprises at least one carbonate salt, most preferably potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, ammonium hydrogen bicarbonate, lithium bicarbonate, ammonium carbonate, or potassium carbonate, or a combination thereof.
  • the formulation when mixed with water, has a pH value between about 9.6 and about 9.8.
  • One embodiment consists substantially of the at least one cationic surfactant, the at least one reactive compound, and the at least one water-soluble bleaching activator.
  • the invention is yet further of a formulation for use in neutralization of at least one toxant, the formulation comprising: a t least one solubilizing compound, selected from the group consisting of a cationic hydrotrope and a fatty alcohol comprising from 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, hydroperoxycarbonate, peracetic acid, sodium perborate, sodium peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and at least one bleaching activator selected from the group consisting of O-acetyl, N-acetyl, and nitrile group bleaching activators; wherein the at least one solubilizing compound, the at least one reactive compound, and the at least one bleaching activator, when mixed with water and exposed to the at least one toxant, neutralizes the at least one toxant.
  • a t least one solubilizing compound
  • kits comprises: a premixed component comprising at least two solubilizing agents; a first component comprising at least one bleaching activator; and a second component comprising at least one reactive compound.
  • the first embodiment may further comprise water and a base
  • the premixed component may additionally comprise a water-soluble polymer
  • the at least one bleaching activator is preferably propylene glycol diacetate, glycerol diacetate, and/or TAED
  • the premixed component may additionally comprise a fatty alcohol comprising from 8 to 20 carbon atoms per molecule
  • the at least one reactive compound may be urea hydrogen peroxide with the second component comprising the at least one reactive compound additionally comprising sodium percarbonate
  • the premixed component may additionally comprise a short-chained alcohol.
  • a second embodiment comprises: a first premixed component comprising at least two solubilizing agents and water; and a second premixed component comprising at least one bleaching activator and the at least one reactive compound, wherein the at least one bleaching activator is in solid form.
  • the first premixed component preferably additionally comprises an acid
  • the at least one bleaching activator preferably comprises acetycholine chloride
  • the at least one reactive compound comprises urea hydrogen peroxide
  • the at least one bleaching activator comprises TAED
  • the at least one bleaching activator is encapsulated to prevent premature reaction with the at least one reactive compound.
  • a third embodiment comprises: a premixed component comprising at least two solubilizing agents and at least one bleaching activator; and a component comprising at least one reactive compound.
  • the premixed component may additionally comprise water and an acid
  • the component comprising the at least one reactive compound may comprise sodium percarbonate and additionally an acid
  • the at least one reactive compound may comprise urea hydrogen peroxide with the component comprising the at least one reactive compound additionally comprising a mixture of potassium carbonate and potassium bicarbonate.
  • the present invention addresses the need for a general formulation that neutralizes the adverse effects of either or both chemical and biological toxants, where a toxant is defined as any chemical or biological compound, constituent, species, or agent that through its chemical or biological action on life processes can, if left untreated, cause death, temporary incapacitation, or permanent harm to humans or animals.
  • a toxant is defined as any chemical or biological compound, constituent, species, or agent that through its chemical or biological action on life processes can, if left untreated, cause death, temporary incapacitation, or permanent harm to humans or animals.
  • Neutralization is defined as the mitigation, detoxification, decontamination, or otherwise destruction of toxants to the extent that the toxants no longer cause acute adverse effects to humans or animals.
  • the formulation and described variations of the present invention can neutralize, and does not itself contain or produce, infection, significant adverse health effects,
  • CW chemical warfare
  • BW biological warfare
  • the present invention also addresses toxants that can cause potential adverse health effects to animals, including humans, where such adverse health effects include infections, acute and chronic health effects, and fatalities.
  • Such toxants can be found in an agricultural facility, animal or dairy farm, or food products processing or packaging facility.
  • the present invention addresses the need for such a formulation that is itself non-toxic and non-corrosive, and that can be delivered by a variety of means and in different phases. Certain embodiments are discussed in U.S. Patent Applications Serial Nos. 09/607,586 and 09/952,940 .
  • the present invention presents additional embodiments that have substantial differences over both the prior art and the earlier embodiments, as will be described below.
  • formulation is defined herein as the activated product or solution (e.g., aqueous solution) that is applied to a surface or body for the purpose of neutralization, with or without the addition of a gas (e.g., air) to create a foam.
  • a gas e.g., air
  • concentrations, constituents, or components listed herein are relative to the weight percentage of the overall activated solution.
  • water is defined herein to broadly include: pure water, tap water, deionized water, demineralized water, saltwater, or any other liquid consisting primarily of H 2 O.
  • One example of a minimum set of constituents for a DF-200 formulation that can achieve a significant rate of spore kill comprises four components:
  • Suitable cationic surfactants include: quaternary ammonium salts and polymeric quaternary salts.
  • suitable quaternary ammonium salts include: cetyltrimethyl ammonium bromide, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyldimethylbenzylammonium salt, and tetrabutyl ammonium bromide.
  • a preferred cationic surfactant is WITCO VARIQUAT 80MCTM, which is a mixture of benzyl (C12-C16) alkyldimethylammonium chlorides.
  • the concentration of quaternary ammonium salt used in DF-200 formulations is preferably no more than about 10%, because at higher concentrations the quaternary ammonium salt becomes significantly toxic to humans and the environment.
  • Suitable cationic hydrotropes include: tetrapentyl ammonium bromide, triacetyl methyl ammonium bromide, and tetrabutyl ammonium bromide.
  • a preferred cationic hydrotrope is WITCO ADOGEN 477TM, which is a pentamethyltallow alkyltrimethylenediammonium dichloride.
  • Suitable fatty alcohols include alcohols having 8-20 carbon atoms per molecule, such as: 1-dodecanol, pure dodecanol, hexadecanol, and 1-tetradecanol.
  • Suitable reactive compounds include: peroxide compounds; hydrogen peroxide; urea hydrogen peroxide; sodium perborate; sodium percarbonate; sodium carbonate perhydrate; sodium peroxypyrophosphate; sodium peroxysilicatehydrogen; peroxide adducts of pyrophosphates; citrates; sodium sulfate; urea; and sodium silicate; an activated peroxide compound (e.g., hydrogen peroxide + bicarbonate); peracetic acid; oximates (e.g., butane-2,3-dione, monooximate ion, and benzohydroxamate); alkoxides (e.g., methoxide and ethoxide); aryloxides (e.g., aryl substituted benzenesulfonates); aldehydes (e.g., glutaraldehyde); peroxymonosulfate; Fenton's reagent (a mixture of iron and peroxide); and sodium hypochlorit
  • hydroxyl ions OH -
  • hydroperoxide ions (OOH - )
  • hydroperoxide ions HCO 4 -
  • Hydroperoxycarbonate ions HCO 4 -
  • its concentration is preferably less than about 10% because higher concentrations are significantly corrosive, especially in the range of 30-50% hydrogen peroxide concentration.
  • a carbonate salt e.g., sodium bicarbonate or potassium bicarbonate
  • a peroxide compound e.g., hydrogen peroxide
  • the added carbonate salt combines with, e.g., hydrogen peroxide to form the highly reactive hydroperoxycarbonate species (HCO 4 - ).
  • Addition of carbonate salts can also buffer the formulation to optimize the pH.
  • a minimum set of constituents for DF-200 formulations that can achieve a very high rate of spore kill can comprise five components:
  • suitable carbonate salts include: potassium bicarbonate, sodium bicarbonate, ammonium bicarbonate, ammonium hydrogen bicarbonate, lithium bicarbonate, ammonium carbonate, and potassium carbonate.
  • Figure 1 shows the results of decontamination tests on Bacillus globigii spores (initial concentration 10 7 spores/ml). The spores were exposed to four different sub-combinations of the various components of DF-200 formulations for 1 hour (the pH of the formulation was 9.8). The degree of spore kill was determined by culturing surviving organisms.
  • spore kill was achieved by using a third combination, comprising (3) an aqueous solution of 2% Variquat (a cationic surfactant), 2% propylene glycol diacetate (bleaching activator), 5% potassium bicarbonate (buffer and peroxide activator) and 2% hydrogen peroxide (oxidant).
  • Variquat a cationic surfactant
  • propylene glycol diacetate a cationic surfactant
  • potassium bicarbonate buffer and peroxide activator
  • hydrogen peroxide oxidant
  • the present invention provides an enhanced decontamination formulation for high foam applications ("DF-200HF").
  • DF-200HF an enhanced decontamination formulation for high foam applications
  • An example of a formulation for DF-200HF comprises:
  • This formulation is effective at a pH value between 7.5 and 10.5. This formulation can be adjusted to a pH value between 9.6 and 9.8 for optimal decontamination of all target agents.
  • This "high-foam” formulation includes a cationic water-soluble polymer (e.g., Jaguar 8000TM), which increases the bulk viscosity of the solution and produces a more stable foam.
  • non-anionic water-soluble polymers examples include: polyvinyl alcohol, guar gum, (cationic or non-ionic) polydiallyl dimethyl ammonium chloride, polyacrylamide, polyethylene glycol 8000 (PEG 8000), and JAGUAR 8000TM (Guar Gum 2-hydroxypropyl ether).
  • a cationic polymer is preferred over a non-ionic polymer; an anionic polymer does not work well.
  • the fatty alcohol 1-dodecanol serves to increase the surface viscosity of the foam lamellae to also increase foam stability against drainage and bubble collapse.
  • the present invention provides an enhanced decontamination formulation for low foam applications ("DF-200LF").
  • DF-200LF an enhanced decontamination formulation for low foam applications
  • An example of a formulation for DF-200LF comprises:
  • This formulation is generally effective at a pH value between 7.5 and 10.5. This formulation can be adjusted to a pH value between about 9.6 and 9.8 for optimal decontamination of all target agents.
  • 'High Foam' refers to the ability of a formulation to form a highly stable and persistent foam, whereas 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 notation "ND” refers to a concentration below detectable limits, and "PGD” refers to propylene glycol diacetate (a preferred bleaching activator).
  • Table 1 Summary of the reaction rates for Mustard simulant (2-Chloroethyl phenyl sulfide).
  • Formulation Mustard Simulant (% Decontaminated) 1 Minute 15 Minutes 60 Minutes DF-100A(pH 8) 18 42 81 DF-100A (pH 9.2) 16 38 83 DF-200HF (2% PGD / 3% H 2 O 2 / 4.5% Bicarb) 42 62 ND DF-200HF (2% PGD / 3.5% H 2 Q 2 /4% Bicarb) 94 98 ND DF-200LF (2.5% PGD/3% H 2 O 2/ 4.5% Bicarb) 55 91 ND Table 2: Summary of the reaction rates for VX simulant (0-Ethyl S-Ethyl Phenylphosphonothioate).
  • Formulation VX Simulant (% Decontaminated) 1 Minute 15 Minutes 60 Minutes DF-100A (pH 10) 45 99 ND DF-100A (pH 9.2) 33 71 93 DF-200HF (2% PGD / 3% H 2 O 2 / 4.5% Bicarb) 63 98 ND DF-200HF (2% PGD / 3.5% H 2 O 2 / 4% Bicarb) 66 99 ND DF-200LF (2.5% PGD / 3% H 2 O 2 / 4.5 Bicarb) 79 98 ND Table 3: Summary of the reaction rates for G Agent simulant (Diphenyl chlorophosphate).
  • Formulated G Agent Simulant (% Decontaminated) 1 Minute 15 Minutes 60 Minutes DF-100A (pH 8) 53 ND ND DF-100A (pH 9.2) ND ND ND DF-200 HF (2% PGD / 3% H 2 O 2 /4.5 Bicarb) ND ND ND DF-200HF (2% PGD / 3.5% H 2 O 2 4% Bicarb) ND ND ND DF-200LF (2.5% PGD / 3% H 2 O 2 4.5% Bicarb) ND ND ND Table 4: Summary of the kill rates for Anthrax simulant (Bacillus globigii spores) Formulation Anthrax Simulant Anthrax Simulant % Kill after 30 Minutes % Kill after 60 Minutes DF-100A (pH 8) 99.99 99.99999 DF-100A (pH 9.2) 90 99.9 DF-200HF (2% PGD / 3% H 2 O 2 / 4.5 Bicarb) 99.99
  • DF-200 and DF-100A Additional differences between DF-200 and DF-100A include:
  • DF-200 formulations e.g., DF-200HF and DF-200LF
  • DF-100A formulations DF-100A formulations
  • a bleaching activator e.g., propylene glycol diacetate
  • Bleaching activators can be compounds with O- or N- bounded acetyl groups that react with the strongly nucleophilic hydroperoxy anion (OOH - ) to yield peroxygenated species, which are more efficient oxidizers than hydrogen peroxide alone.
  • TAED and NOBS bleaching activators are extremely insoluble in water (e.g., TAED is only 0.1% soluble at 25°C). To get around this problem in a laundry detergent, the solid TAED or NOBS particles are kept in suspension by the agitating action of the washing machine, where they slowly react with the hydrogen peroxide in the detergent.
  • agitation in the field of DF-200 formulations presents practical problems; hence, a water-soluble bleaching activator is preferred.
  • Useful water-soluble bleaching activators include short-chained organic compounds that contain an ester bond, e.g., 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.
  • a preferred water-soluble bleaching activator is propylene glycol diacetate (PGD), which is shown below.
  • This molecule reacts with hydroperoxy anions (OOH - ), giving up the ester bonds to form two peroxygenated molecules.
  • Propylene glycol diacetate also acts as an organic solvent that is highly effective in solubilizing insoluble organic molecules (e.g., chemical warfare agents, as well as foam stabilizers/boosters (such as 1-dodecanol and Lauramide DEA)). Therefore, an added function of this compound is that it can be used to supplement the diethylene glycol monobutyl ether (DEGMBE) solvent that is 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 the propylene glycol diacetate to serve a dual purpose (i.e., solvent and bleaching activator).
  • DEGMBE diethylene glycol monobutyl ether
  • Di(propylene glycol) methyl ether solvent used in some DF-200 formulations
  • Bleaching activators are generally not stable in water for long periods of time. This is especially true when the aqueous solution is at a high pH (>10). Therefore, for long shelf life, the propylene glycol diacetate (or other bleaching activator) is preferably stored separate from the aqueous solution until use. This is not unlike other products that utilize bleach activators (e.g., laundry detergents), where all the components of the formulation are kept dry and separated until use (in the case of laundry detergent, the bleaching activator is encapsulated to prevent it from reacting with the peroxide component until both components are mixed in water).
  • bleach activators e.g., laundry detergents
  • ethylene glycol diacetate Another example of a water-soluble bleaching 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., anti-freeze), which is a relatively toxic byproduct. Propylene glycol diacetate, on the other hand, does not form this relatively toxic byproduct.
  • the present invention is also of a non-foaming embodiment ("DF-200NF") that may be used for specific applications, e.g., the kill of biological organisms, batch processing (such as in chemical agent demilitarization neutralization processes, i.e., in a bath of solution), or spray applications.
  • DF-200NF non-foaming embodiment
  • a preferred example of this formulation comprises (amounts illustrative):
  • the formulation can be adjusted to a pH value between about 9.6 and 9.8 for optimum performance, and is effective for decontamination of all target agents.
  • the present invention is also of an enhanced version of DF-100A that utilizes the propylene glycol diacetate bleaching activator.
  • a preferred embodiment of this enhanced formulation, (“DF-100E") comprises (amounts illustrative):
  • This formulation can be adjusted to a pH value between about 9.6 and 9.8 for optimal performance against all agents.
  • the performance of DF-100E (2% PGD / 3.00% H 2 O 2 / 3.75% Bicarbonate salt) against chemical simulants is shown below in Table 5: Table 5: Summary of the reaction rates for the DF-100E formulation in kinetic testing. Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard (HD) 83 92 ND G Agents ND ND ND VX 66 96 ND
  • 2-part, 3-part, and 4-part “kit” configurations are shown for the different embodiments of DF-200 formulations.
  • the 2-part and 3-part kits have the bulk of the water already "pre-packaged” in one of the two (or three) containers (usually the foam component). This allows for rapid deployment of the decontamination solution, the use of small-scale units (e.g., backpacks), and doesn't require any extra water to be provided in the field.
  • the 4-part kits generally require that the make-up water is added in the field at, or near, the site of contamination. This allows the "package" containing the other three parts to be much lighter, which makes it easier to ship and store. However, a source of make-up is required in the field (which can be saltwater).
  • the DF-200 formulations can be configured either way, with the bulk of the water “pre-packaged", or without, depending on the application.
  • the DF-200HF formulation can be configured as a 4-part kit, and then prepared for field use as follows (amounts illustrative):
  • Part A (Foam Concentrate):
  • Part B Solid Component
  • the bulk of the 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.
  • the make-up water (Part D) would be supplied in the field at, or near, the site of contamination.
  • the pH of the formulation can be adjusted to be between about 9.6 and 9.8 for optimal performance.
  • the formulation as described above will produce 1 liter of "high" foam solution.
  • sodium percarbonate supplies a portion of the hydrogen peroxide, a portion of the bicarbonate, and a base for buffering the solution.
  • the remainder of the hydrogen peroxide is supplied by the urea hydrogen peroxide.
  • the total hydrogen peroxide concentration is approximately 3% in this example.
  • the viscosity of the formulation can be adjusted to be between about 4-9 mm 2 /s.
  • activated DF-200 formulations are used preferably within 8 hours after mixing, however, they still can be effective for up to 24 hours and longer.
  • DF-200HF High Foam
  • DF-200LF Low Foam
  • DF-200LF Low Foam
  • DF-200LF Low Foam
  • it can be applied to a surface, left for a relatively short period of time (e.g., 15-60 minutes), and then rinsed off with a high pressure freshwater or salt water spray. This will minimize corrosion of the material to which it is applied, which will make it especially useful for decontaminating aircraft and other equipment where corrosion is a concern. It will also minimize the time required for decontamination, which is especially advantageous for military use (on the battlefield or at fixed sites).
  • Saltwater can also be effectively used as the make-up water (Part D) for DF-200 formulations.
  • the table below shows the results of kinetic tests using DF-200HF (2% PGD / 3.50% H 2 0 2 / 4.0% Bicarbonate salt) with saltwater ( ⁇ 35,000 ppm total dissolved solids):
  • Table 7 Summary of the reaction rates for DF-200HF formulation (2% PGD / 3.5% H 2 O 2 / 4.0% Bicarbonate salt) with saltwater used as the make-up water (Part D).
  • Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard 24 42 89 G Agents ND ND ND VX 62 96 >99
  • Results demonstrate more effective decontamination of the test coupon as compared to DF-100A.
  • Table 8 Results of Surface Testing of DF-200HF on CARC. Decon Formulation mg VX Simulant (Unreacted simulant on surface after 60 minutes) Mg Mustard Simulant (Unreacted simulant on surface after 60 minutes) Control 8.0 ⁇ 0.3 8.0 ⁇ 0.3 DF-100A (pH 9.2) 2.9 4.5 DF-200HF (2% PGD / 3.5% H 2 O 2 / 4.0% Bicarb) 1.4 2.5
  • Insoluble bleach activators such as TAED, NOBS, and N-acetyl glucosamine
  • TAED TAED
  • NOBS NOBS
  • the formulation results in a slurry when mixed with water, instead of a true aqueous solution.
  • the present invention also provides a method to utilize a water-insoluble solid bleach activator (e.g., TAED) to produce a reactive slurry (wherein a slurry is defined as a watery mixture that includes insoluble, undissolved matter).
  • a slurry is defined as a watery mixture that includes insoluble, undissolved matter.
  • DF-200HF Slurry is a modification of the DF-200HF formulation.
  • An example of a 4-part kit configuration is shown below (amounts illustrative):
  • Part A (Foam Concentrate):
  • Part B Solid Component
  • the formulation as described above will produce 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between about 9.6 and 9.8 for optimal performance.
  • the following mixing procedure can be used: Mix Part B into Part D. Then, add Parts C and A to Parts B+D. Use, preferably, within 8 hours.
  • Table 9 Summary of the reaction rates for the DF-200HF Slurry formulation in kinetic testing. Note that improved performance can be achieved by using higher concentrations of TAED (e.g., 2% TAED, instead of 1% TAED). Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard (HD) 67 96 ND G Agents ND ND ND VX 33 95 ND
  • DF-200 would typically be used in large-scale operations where dedicated deployment equipment and a source of make-up water is readily available (e.g., for use by the military to decontaminate 'fixed sites' such as airbases and seaports), or used to minimize the volume of 'pre-packaged' water in order to minimize the weight of the formulation that needs to be shipped and stored.
  • the present invention is also of configurations emphasizing the rapid deployment of DF-200 formulations, and/or its deployment using small-scale deployment equipment (such as hand-held units, backpack units, or units mounted on small dollies). For these applications, all of the water is 'pre-packaged' into the formulation, so that no extra water is required in the field.
  • a first example of a 3-part kit configuration for a Rapid Deployment version of DF-200HF, "DF-200HF Rapid Deployment #1”, comprises (amounts illustrative):
  • Part A (Liquid Foam Component):
  • Part B Solid Oxidant Component
  • Part C Liquid Bleaching Activator
  • This configuration will produce 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between about 9.6 and 9.8 for optimal performance.
  • the following mixing procedure can be used: Mix Part B into Part A. After dissolution of the urea hydrogen peroxide, add Part C to Part A+B. Use, preferably, within 8 hours.
  • Table 10 The performance of DF-200HF Rapid Deployment against chemical agent simulants is shown below in Table 10: Table 10: Reaction rates from kinetic testing of DF-200HF Rapid Deployment #1 configuration. Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard (HD) 48 82 ND G Agents ND ND ND VX 71 97 >99
  • FIG. 2 A schematic example of a preferred mixing procedure for this first example of a rapid deployment configuration of DF-200HF is shown in Figure 2 .
  • Urea hydrogen peroxide dissolves rapidly in water. Therefore, the formulation can be prepared and deployed in a very short time at the scene of an incident involving chemical or biological warfare agents, making it ideal for use by civilian first responders (firefighters, HazMat units, police officers, and others who would be the first to arrive at the location of a CBW attack), and/or the military.
  • the particular bleaching activator (propylene glycol diacetate) used in this formulation is not stable in an aqueous solution where the pH is greater than approximately 9.9. Therefore, it is important to mix the right components in the correct order. For example, if Part C is mixed into Part A before the addition of Part B, there may be some loss of activity in DF-200HF since the propylene glycol diacetate is exposed to a solution having a pH value >9.9. This is not true, however, if Part B is added to Part A before the addition of Part C, since the addition of Part B to Part A brings the pH of the Part A+B mixture to a value below about 9.9.
  • the solvent, diethylene glycol monobutyl ether, used in Part A (the foam solution) of the first example shown above for DF-200HF Rapid Deployment #1 is different than the solvent that was used in the previously described DF-200HF formulation (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 rapid deployment configuration. Also, note that a short-chained alcohol (i.e., isobutanol) has been added to the foam component (Part A) in the rapid deployment configuration #1 of DF-200HF.
  • a short-chained alcohol i.e., isobutanol
  • a preferred formulation for DF-200HF Rapid Deployment #1 comprises:
  • the formulation can be adjusted to a pH value between about 9.6 and 9.8 for optimal performance, and is effective for decontamination of all target agents.
  • a second example of a 3-part kit configuration for a Rapid Deployment version of DF-200HF, "DF-200HF Rapid Deployment #2”, comprises (amounts illustrative):
  • the present invention is also of a 2-part kit configuration of a rapid deployment embodiment of the DF-200HF Slurry embodiment ("DF-200HF Slurry Rapid Deployment"), in which TAED (or other solid peroxide activator) is utilized as the bleaching activator.
  • DF-200HF Slurry Rapid Deployment a rapid deployment configuration of the DF-200HF Slurry embodiment
  • TAED solid peroxide activator
  • Part A (Liquid Foam Component):
  • Part B Solid Oxidant and Bleaching Activator
  • This formulation will produce 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between 9.6 and 9.8 for optimal performance.
  • the following procedure can be used to mix the formulation: Mix Part B into Part A. Then, wait for at least one minute before use to allow time for the TAED to react with the hydrogen peroxide. Use, preferably, within 8 hours. It is useful to note that TAED will not immediately dissolve in water, but will remain as solid particles for at least 15-20
  • Part A (Liquid Foam Component):
  • Part B Solid Oxidant Component
  • Part C Liquid Bleaching Activator
  • Polyethylene Glycol 8000 polymer replaced the poly (Ethylene Oxide) polymer used in DF-200HF Rapid Deployment #1 as a water-soluble polymer.
  • Hexylene Glycol replaced Diethylene Glycol Monobutyl Ether and Isobutanol used as a solvents.
  • Glycol Diacetate i.e., Diacetin replaced Propylene Glycol Diacetate used as the bleaching activator.
  • the present invention is also of a 2-part kit configuration of a rapid deployment embodiment of the DF-200HF Slurry embodiment ("DF-200HF Slurry Rapid Deployment"), in which TAED (or other solid peroxide activator) is utilized as the bleaching activator.
  • DF-200HF Slurry Rapid Deployment a rapid deployment configuration of the DF-200HF Slurry embodiment
  • TAED solid peroxide activator
  • Part A (Liquid Foam Component):
  • Part B Solid Oxidant and Bleaching Activator
  • This formulation will produce 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between 9.6 and 9.8 for optimal performance.
  • the following procedure can be used to mix the formulation: Mix Part B into Part A. Then, wait for at least one minute before use to allow time for the TAED to react with the hydrogen peroxide. Use, preferably, within 8 hours. It is useful to note that TAED will not immediately dissolve in water, but will remain as solid particles for at least 15-20 minutes. Therefore, a filter or screen may be required so that the undissolved TAED particles will not damage or clog any pumps or other components of the deployment device. However, the formulation is ready for use approximately 1 minute after addition of the TAED particles in Part B to Part A.
  • TAED it is useful to employ an encapsulated form of TAED in this configuration for two reasons.
  • the protective coating (which slowly dissolves in water) will protect the TAED so that it will not react with the urea hydrogen peroxide during storage.
  • the coating will protect the TAED from the high pH conditions in Part A until the urea hydrogen peroxide dissolves and lowers the pH of the formulation to a value below approximately 9.9.
  • TAED should be used in a similar manner as propylene glycol diacetate with respect to protecting the activator against exposure to high pH solutions. TAED will lose much of its effectiveness as a bleaching activator if it is exposed to solutions with a pH greater than 9.9.
  • FIG. 3 A schematic illustrating an example of a process for field mixing DF-200HF Slurry Rapid Deployment is shown in Figure 3 .
  • the present invention is also of a method for preparing the foam component (Part A) of the rapid deployment configurations.
  • Part A foam component
  • the invention is also of the following alternative DF-200 formulations:
  • Part A (Liquid Foam Component):
  • This formulation will produce 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between about 9.6 and 9.8 for optimal performance.
  • a person of ordinary skill in the art will understand 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 about 9.6 to about 9.8).
  • the potassium carbonate serves as both a base and a source of carbonate/bicarbonate.
  • To prepare this formulation mix Part B into Part A. Use, preferably, within 8 hours.
  • Table 12 Reaction rates from kinetic testing for DF-200HF with propylene glycol against chemical agent simulants is shown in Table 12.
  • Table 12 Reaction rates from kinetic testing for DF-200HF with propylene glycol (first example). Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard (HD) 16 80 ND G Agents ND ND ND VX 66 90 >99
  • This configuration also incorporates the bleaching 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 of pH greater than 3, but is hydrolytically stable in solutions of pH less than 3.
  • This configuration also uses the polyethylene glycol polymer (PEG 8000) for viscosity enhancement. This polymer is used in many cosmetics and is extremely soluble and stable in water. In addition, it is easier to mix into solution than Jaguar 8000 or a high molecular weight poly(ethylene oxide), since it does not have the tendency to clump.
  • PEG 8000 polyethylene glycol polymer
  • This configuration includes propylene glycol as a freeze-point depressant.
  • Propylene glycol is considered to be an environmentally friendly antifreeze. In this case, the concentration is approximately 15% by weight, which lowers the freezing point of Part A to approximately -20°C.
  • This configuration has also been tested with good results with propylene glycol concentrations as high as 40% by weight.
  • Part A (Liquid Foam Component):
  • This formulation will produce 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between about 9.6 and 9.8 for optimal performance.
  • the following mixing procedure can be used: Mix Part B into Part A. Use, preferably, within 8 hours.
  • sodium bisulfate (a common pool conditioning chemical), or other acid can be used in place of citric acid to adjust the pH.
  • Table 13 Reaction rates from kinetic testing for the second example of DF-200HF with proplyene glycol (utilizing sodium percarbonate). Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard (HD) 80 ND ND VX 76 96 >99
  • sodium percarbonate dissolves much more slowly than urea hydrogen peroxide after it has been added to Part A.
  • sodium percarbonate can be milled to approximately a 100 mesh size for use in this configuration. The time to dissolve the sodium percarbonate was decreased from approximately 30 minutes to about 2 minutes when milled sodium percarbonate was used.
  • Corrosion inhibitors can be added to DF-200 formulations to reduce their corrosivity.
  • a preferred corrosion inhibitor for use in DF-200 formulations is N,N-dimethyl ethanolamine.
  • other corrosion inhibitors such as triethanolamine, ethanolamine salts of C9, C10, and C12 diacid mixtures, dicyclohexyl amine nitrite, and N,N-dibenzylamine, can be used.
  • the Corrosion inhibitors added to DF-200 formulations can serve multiple purposes:
  • An example of a 3-part kit configuration of DF-200HF with a corrosion inhibitor comprises (amounts illustrative):
  • Part A (Liquid Foam Component):
  • Part B Solid Oxidant Component
  • Part C Liquid Bleaching Activator
  • This formulation will produce 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between about 9.6 and 9.8 for optimal performance.
  • the following mixing procedure can be used: Mix Part B into Part A. Then, after dissolution of the urea hydrogen peroxide, add Part C to Part A+B. Use, preferably, within 8 hours.
  • the performance of DF-200HF with corrosion inhibitor is shown below against chemical agent simulants is given in Table 14. Table 14: Reaction rates in kinetic testing for DF-200HF with a corrosion inhibitor. Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard (HD) 7 41 79 VX 58 94 99
  • Tests against the anthrax spore simulant demonstrated 99.9999% (7-Log) kill after a 60 minute exposure to DF-200HF with a corrosion inhibitor.
  • the addition of the corrosion inhibitor has a detrimental effect on the performance of DF-200 against chemical agents, but has no measured effect on the performance of DF-200HF against biological agents. Similar results were obtained when an alternative corrosion inhibitor, 1% triethanolamine, was used.
  • glycerol may be employed as a viscosity builder in place of Jaguar 8000, poly (ethylene oxide), or polyethylene glycol.
  • Glycerol is a common ingredient in cosmetics, where it is used a viscosity builder, as well as a solvent, humectant and emollient.
  • the use of glycerol in DF-200 formulations can serve multiple purposes:
  • An example of a 3-part kit configuration of DF-200HF with glycerol comprises (amounts illustrative):
  • Part A (Liquid Foam Component):
  • Part B Solid Oxidant Component
  • Part C Liquid Bleaching Activator
  • This formulation will produce 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between about 9.6 and 9.8 for optimal performance.
  • the following mixing procedure can be used: Mix Part B into Part A. Then after dissolution of the urea hydrogen peroxide, add Part C to Part +/B. Use, preferably, within 8 hours.
  • the performance of DF-200HF with glycerol against chemical agent simulants is given in Table 15. Table 15: Reaction rates in kinetic testing for DF-200HF with glycerol. Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard (HD) 63 96 ND G Agents ND ND ND VX 76 99 ND
  • This formulation can be used for direct application to humans because the glycerol will act as a humectant.
  • This formulation could also be utilized, e.g., as a spray or shower, by removing foaming constituents (such as 1-dodecanol and Adogen 477), and by reducing the concentration of peroxide.
  • foaming constituents such as 1-dodecanol and Adogen 477
  • concentration of peroxide such as 1-dodecanol and Adogen 477
  • Propylene glycol diacetate a bleaching activator used in many of the previously described DF-200 configurations is not presently available in solid form. However, other bleaching activators are available in solid form.
  • Solid O-acetyl bleaching activators e.g., acetylcholine chloride, which is often used in eyedrop solutions
  • acetylcholine chloride which is often used in eyedrop solutions
  • DF-200 formulations in place of (liquid) propylene glycol diacetate.
  • the chemical structure of this O-acetyl bleaching activator is shown below. As can be seen, the molecule contains an O-acetyl group that can activate peroxide, and it is a quaternary compound, which is very compatible with DF-200 formulations.
  • Acetylcholine chloride is also soluble in water and is very hygroscopic.
  • An example of a 2-part kit configuration of DF-200HF using acetylcholine chloride comprises (amounts illustrative):
  • Part A (Liquid Foam Component):
  • This formulation will produce approximately 1 liter of foam solution.
  • the pH of the final formulation can be adjusted to be between about 9.6 and 9.8 for optimal performance.
  • mix Part B into Part A. Use, preferably, within 8 hours.
  • Table 16 The performance of DF-200HF using acetylcholine chloride against chemical agent simulants is shown in Table 16.
  • Table 16 Reaction rates from kinetic testing for the DF-200HF using acetylcholine chloride as an activator. Simulant % Decontaminated 1 Minute 15 Minutes 60 Minutes Mustard (HD) 60 98 ND VX 10 85 >99
  • Tests were also conducted to determine the minimum constituents required for spore kill in a DF-200 formulation which utilizes peracetic acid as an oxidant. These results indicate that only three constituents, i.e., peracetic acid, bicarbonate and the cationic surfactant, are necessary to achieve high rates of spore kill.
  • Results of tests against anthrax spores is shown in Tables 20 and 21 and against Yersinia pestis (i.e., the plague bacterium) are shown in Table 22 (NG refers to 'no growth').
  • the detection limit for these tests were 10 CFU/ml. Note that the 'error bars' in the '% Reduction' column takes into account this detection limit.
  • Table 20 Kill rates for B. anthracis AMES-RIID spores in a solution of DF-200HF.
  • the petri dishes used for cell growth on each of these tests were saved for 21 days following the tests to verify that DF-200HF had actually killed the spores, rather than just inhibiting their growth. No growth on any of the petri dishes was observed after the 21-day period.
  • TICs toxic industrial chemicals
  • Table 23 Summary of Toxic Industrial Chemical (TIC) Neutralization Tests with DF-200HF.
  • TIC % Decontaminated 1 minute 15 minutes 60 minutes Malathion (liquid) 89 95 Below Detection Hydrogen Cyanide (gas) >99 >99 >99 Sodium Cyanide (solid) 93 98 >99 Butyl Isocyanate (liquid) 99 Below Detection Below Detection Carbon Disulfide (liquid) >99 >99 Below Detection Phosgene (gas) 98 >99 >99

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Claims (32)

  1. Formulation destinée à une utilisation dans la neutralisation d'au moins un agent toxique, ladite formulation comprenant :
    - au moins un composé solubilisant, choisi dans le groupe constitué par un hydrotrope cationique et un alcool gras comprenant de 8 à 20 atomes de carbone par molécule ;
    - au moins un composé réactif, où ledit au moins un composé réactif est choisi dans le groupe constitué par le peroxyde d'hydrogène, le peroxyde d'hydrogène-urée, l'hydroperoxycarbonate, l'acide peracétique, le perborate de sodium, le peroxypyrophosphate de sodium, le peroxysilicate de sodium, et le percarbonate de sodium ; et
    - au moins un activateur de blanchiment hydrosoluble choisi dans le groupe constitué par l'acétate de monométhyléther et de propylène glycol, l'acétate de méthyle, le glutarate de diméthyle, l'acétate de monoéthyléther et de diéthylène glycol, et le diacétate de propylène glycol, et des combinaisons de ceux-ci ;
    dans laquelle ledit au moins un composé solubilisant, ledit au moins un composé réactif, et ledit au moins un activateur de blanchiment, lors de leur mélange avec de l'eau et l'exposition au au moins un agent toxique, neutralisent le au moins un agent toxique.
  2. Formulation selon la revendication 1, comprenant au moins deux composés solubilisants, où au moins un composé solubilisant est un agent tensioactif cationique et au moins un composé solubilisant est un hydrotrope cationique ; et
    où lesdits au moins deux composés solubilisants, ledit au moins un composé réactif, et ledit au moins un activateur de blanchiment hydrosoluble, lors de leur mélange avec de l'eau et l'exposition au au moins un agent toxique, neutralisent le au moins un agent toxique.
  3. Formulation selon la revendication 2, dans laquelle ledit agent tensioactif cationique comprend un sel d'ammonium quaternaire.
  4. Formulation selon la revendication 3, dans laquelle ledit sel d'ammonium quaternaire est choisi dans le groupe constitué par le bromure de cétyltriméthylammonium, le chlorure de benzalkonium, le chlorure de benzéthonium, le chlorure de cétylpyridinium, un sel d'alkyldiméthylbenzylammonium, le bromure de tétrabutylammonium, et un mélange de chlorures de benzyl(C12-C16)alkyldiméthylammonium.
  5. Formulation selon la revendication 2, comprenant en outre un polymère hydrosoluble.
  6. Formulation selon la revendication 5, dans laquelle le polymère hydrosoluble est choisi dans le groupe constitué par l'alcool polyvinylique, la gomme guar, le chlorure de polydiallyl diméthylammonium (cationique ou non ionique), le polyacrylamide, le poly(oxyde d'éthylène), le glycérol, le polyéthylène glycol 8000 (PEG 8000) et le JAGUAR 8000 ohm (2-hydroxypropyléther de gomme guar), et des combinaisons de ceux-ci.
  7. Formulation selon la revendication 2, comprenant en outre un alcool gras comprenant de 8 à 20 atomes de carbone par molécule.
  8. Formulation selon la revendication 2, comprenant en outre un solvant.
  9. Formulation selon la revendication 8, dans laquelle le solvant comprend un élément du groupe constitué par le di(propylène glycol) méthyléther et le diéthylène glycol monobutyléther, et une combinaison de ceux-ci.
  10. Formulation selon la revendication 2, comprenant en outre un sel de carbonate.
  11. Formulation selon la revendication 10, dans laquelle le sel de carbonate est choisi dans le groupe constitué par le bicarbonate de potassium, le bicarbonate de sodium, le bicarbonate d'ammonium, l'hydrogénocarbonate d'ammonium, le bicarbonate de lithium, le carbonate d'ammonium, et le carbonate de potassium, et des combinaisons de ceux-ci.
  12. Formulation selon la revendication 2, dans laquelle ledit au moins un activateur de blanchiment est le diacétate de propylène glycol.
  13. Formulation selon la revendication 2, où la formulation, lors de son mélange avec de l'eau, possède une valeur de pH comprise entre environ 9,6 et environ 9,8.
  14. Configuration en kit, comprenant :
    un composant prémélangé comprenant un agent tensioactif cationique et un hydrotrope cationique,
    un premier composant comprenant au moins un activateur de blanchiment hydrosoluble choisi dans le groupe constitué par le diacétate d'éthylène glycol, l'acétate de monométhyléther et de propylène glycol, l'acétate de méthyle, le glutarate de diméthyle, l'acétate de monoéthyléther et de diéthylène glycol, et le diacétate de propylène glycol, et des combinaisons de ceux-ci ;
    un deuxième composant comprenant au moins un composé réactif choisi dans le groupe constitué par le peroxyde d'hydrogène, le peroxyde d'hydrogène-urée, l'hydroperoxycarbonate, l'acide peracétique, le perborate de sodium, le peroxypyrophosphate de sodium, le peroxysilicate de sodium, et le percarbonate de sodium ;
    où lesdits composants, lors de leur mélange avec de l'eau, forment une formulation de décontamination destinée à neutraliser les agents toxiques.
  15. Configuration en kit selon la revendication 14, comprenant en outre de l'eau et une base.
  16. Configuration en kit selon la revendication 14, dans laquelle ledit composant prémélangé comprend en outre un polymère hydrosoluble.
  17. Configuration en kit selon la revendication 14, dans laquelle ledit au moins un activateur de blanchiment est le diacétate de propylène glycol.
  18. Configuration en kit selon la revendication 14, dans laquelle ledit composant prémélangé comprend en outre un alcool gras comprenant de 8 à 20 atomes de carbone par molécule.
  19. Configuration en kit selon la revendication 14, dans laquelle ledit au moins un composé réactif comprend du peroxyde d'hydrogène-urée et où ledit deuxième composant comprenant ledit au moins un composé réactif comprend du percarbonate de sodium.
  20. Configuration en kit selon la revendication 14, dans laquelle ledit composant prémélangé comprend en outre un alcool à chaîne courte.
  21. Configuration en kit selon la revendication 14, comprenant
    ledit composant prémélangé comprenant ledit agent tensioactif cationique et ledit hydrotrope cationique et comprenant en outre de l'eau ; et
    un deuxième composant prémélangé comprenant un mélange dudit au moins un activateur de blanchiment et dudit au moins un composé réactif, où ledit au moins un activateur de blanchiment se trouve sous forme solide.
  22. Configuration en kit selon la revendication 21, dans laquelle ledit premier composant prémélangé comprend en outre un acide.
  23. Configuration en kit selon la revendication 14, où ladite configuration en kit comprend :
    un composant prémélangé comprenant un mélange desdits au moins deux agents solubilisants et dudit au moins un activateur de blanchiment ; et
    un composant comprenant ledit au moins un composé réactif.
  24. Configuration en kit selon la revendication 23, dans laquelle ledit composant prémélangé comprend en outre de l'eau et un acide.
  25. Configuration en kit selon la revendication 23, dans laquelle ledit composant comprenant ledit au moins un composé réactif comprend du percarbonate de sodium et comprend en outre un acide.
  26. Configuration en kit selon la revendication 23, dans laquelle ledit au moins un composé réactif comprend du peroxyde d'hydrogène-urée et où ledit composant comprenant ledit au moins un composé réactif comprend en outre un mélange de carbonate de potassium et de bicarbonate de potassium.
  27. Formulation destinée à une utilisation dans la neutralisation d'au moins un agent toxique selon la revendication 2, ladite formulation comprenant :
    - au moins un agent tensioactif cationique et au moins un hydrotrope cationique ;
    - au moins un sel de carbonate choisi dans le groupe constitué par le bicarbonate de potassium, le bicarbonate de sodium, le bicarbonate d'ammonium, l'hydrogénocarbonate d'ammonium, le bicarbonate de lithium, le carbonate d'ammonium, et le carbonate de potassium, et des combinaisons de ceux-ci ;
    - au moins un composé réactif, où ledit au moins un composé réactif est choisi dans le groupe constitué par le peroxyde d'hydrogène, le peroxyde d'hydrogène-urée, l'hydroperoxycarbonate, l'acide peracétique, le perborate de sodium, le peroxypyrophosphate de sodium, le peroxysilicate de sodium, et le percarbonate de sodium ;
    - au moins un activateur de blanchiment hydrosoluble choisi dans le groupe constitué par le diacétate d'éthylène glycol, l'acétate de monométhyléther et de propylène glycol, l'acétate de méthyle, le glutarate de diméthyle, l'acétate de monoéthyléther et de diéthylène glycol, et le diacétate de propylène glycol, et des combinaisons de ceux-ci ; et
    dans laquelle ledit au moins un agent tensioactif, ledit au moins un composé réactif, et ledit au moins un activateur de blanchiment hydrosoluble, lors de leur mélange avec de l'eau et l'exposition au au moins un agent toxique, neutralisent le au moins un agent toxique.
  28. Formulation selon la revendication 27, dans laquelle ledit agent tensioactif cationique comprend un sel d'ammonium quaternaire.
  29. Formulation selon la revendication 28, dans laquelle ledit sel d'ammonium quaternaire comprend du chlorure de benzalkonium.
  30. Formulation selon la revendication 27, où la formulation, lors de son mélange avec de l'eau, possède une valeur de pH comprise entre environ 9,6 et environ 9,8.
  31. Formulation selon la revendication 27, constituée sensiblement dudit au moins un agent tensioactif cationique, dudit au moins un sel de carbonate, dudit au moins un composé réactif, et dudit au moins un activateur de blanchiment hydrosoluble.
  32. Formulation selon la revendication 31, constituée sensiblement
    - de 1-10% de chlorure de benzalkonium ;
    - de 1-8% de diacétate de propylène glycol ;
    - de 1-16% de peroxyde d'hydrogène ;
    - de 2-8% de bicarbonate de potassium ; et
    - qsp d'eau.
EP02775899.4A 2001-10-01 2002-09-20 Formulations ameliorees permettant de neutraliser des substances toxiques chimiques, biologiques et industrielles Expired - Lifetime EP1434625B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
US32650801P 2001-10-01 2001-10-01
US326508P 2001-10-01
US33427101P 2001-11-30 2001-11-30
US334271P 2001-11-30
US38710402P 2002-06-07 2002-06-07
US387104P 2002-06-07
PCT/US2002/029886 WO2003028429A2 (fr) 2001-10-01 2002-09-20 Formulations ameliorees permettant de neutraliser des substances toxiques chimiques, biologiques et industrielles

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EP1434625A2 EP1434625A2 (fr) 2004-07-07
EP1434625A4 EP1434625A4 (fr) 2010-07-21
EP1434625B1 true EP1434625B1 (fr) 2018-07-18

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EP (1) EP1434625B1 (fr)
JP (1) JP4582514B2 (fr)
KR (1) KR100916328B1 (fr)
CN (1) CN1612766B (fr)
AU (1) AU2002341750B2 (fr)
BR (1) BR0213019B1 (fr)
CA (1) CA2461872C (fr)
EA (1) EA009242B1 (fr)
HK (1) HK1073618A1 (fr)
IL (2) IL161200A0 (fr)
MX (1) MXPA04003037A (fr)
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EP1928946A2 (fr) 2005-01-11 2008-06-11 Clean Earth Technologies, LLC Formulations destinees a la decontamination de produits chimiques toxiques
US8110538B2 (en) * 2005-01-11 2012-02-07 Biomed Protect, Llc Peracid/peroxide composition and use thereof as an anti-microbial and a photosensitizer
US9700644B2 (en) 2006-08-15 2017-07-11 American Sterilizer Company One part, solids containing decontamination blend composition
US9724550B2 (en) 2006-08-15 2017-08-08 American Sterilizer Company One part, solids containing decontamination blend composition
US20120141598A1 (en) * 2008-10-08 2012-06-07 Jessie Kater Broad spectrum decontaminate and dispersement system
US8969283B2 (en) * 2009-02-05 2015-03-03 American Sterilizer Company Low odor, hard surface sporicides and chemical decontaminants
RU2484868C2 (ru) * 2009-04-24 2013-06-20 Ольга Анатольевна Афанасьевская Комплексная, безотходная переработка токсичных отходов
US20110177145A1 (en) * 2009-07-27 2011-07-21 E.I. Du Pont De Nemours And Company In situ preparation of peracid-based removable antimicrobial coating compositions and methods of use
GB201010374D0 (en) 2010-06-21 2010-08-04 Mtp Innovations Ltd Disinfectant composition
EP3190883A1 (fr) 2014-09-09 2017-07-19 Lonza Inc. Composition désinfectante contenant des composés d'ammonium quaternaire
EA026955B1 (ru) * 2015-03-16 2017-06-30 Общество с ограниченной ответственностью "ФАРМА-ПОКРОВ" Дезинфицирующая композиция
JP6639099B2 (ja) * 2015-03-24 2020-02-05 花王株式会社 酸化性組成物
CA2992543C (fr) * 2015-07-17 2023-09-19 Next Science IP Holdings Pty Ltd Composition antimicrobienne efficace contre les endospores
JP7102008B2 (ja) * 2017-06-15 2022-07-19 ディコン７ システムズ インク 浄化製剤
WO2019018347A2 (fr) * 2017-07-17 2019-01-24 Tiax Llc Compositions de neutralisation et leurs procédés d'utilisation
CN111868220A (zh) * 2018-01-17 2020-10-30 涤康7号系统股份公司 洗衣净化配制物
CN110150279B (zh) * 2019-06-03 2023-08-25 南通思锐生物科技有限公司 一种即时快速生成过氧乙酸消毒剂的配制方法
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JP2005504856A (ja) 2005-02-17
EA009242B1 (ru) 2007-12-28
BR0213019B1 (pt) 2011-12-27
CN1612766B (zh) 2010-10-13
JP4582514B2 (ja) 2010-11-17
WO2003028429A3 (fr) 2003-12-18
KR100916328B1 (ko) 2009-09-11
MXPA04003037A (es) 2005-07-01
BR0213019A (pt) 2004-10-05
EP1434625A2 (fr) 2004-07-07
CA2461872C (fr) 2013-11-26
WO2003028429A2 (fr) 2003-04-10
IL161200A (en) 2007-09-20
CN1612766A (zh) 2005-05-04
IL161200A0 (en) 2004-08-31
EP1434625A4 (fr) 2010-07-21
EA200400500A1 (ru) 2004-10-28
AU2002341750B2 (en) 2007-10-11
KR20040048923A (ko) 2004-06-10
HK1073618A1 (en) 2005-10-14
CA2461872A1 (fr) 2003-04-10

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