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(12) Patent Application Publication (10) Pub. No.: US 2008/0299161 A1 Sanderson (43) Pub

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(12) Patent Application Publication (10) Pub. No.: US 2008/0299161 A1 Sanderson (43) Pub US 200802991 61A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0299161 A1 Sanderson (43) Pub. Date: Dec. 4,9 2008 (54) SOLID BIOCIDE COMPOSITION AND Related U.S. Application Data SEALED BOCDE ARTICLE (60) Provisional application No. 60/750,786, filed on Dec. (76) Inventor: William D. Sanderson, San 16, 2005, provisional application No. 60/812,632, Francisco, CA (US) filed on Jun. 12, 2006. Correspondence Address: Publication Classification MANELLIDENISON & SELTER 2000 MSTREET NW SUITE 700 (51) Int. Cl. WASHINGTON, DC 20036-3307 (US) AOIN 25/34 (2006.01) AOIN 59/08 (2006.01) (21) Appl. No.: 12/091,785 AOIP 5/00 (2006.01) (22) PCT Filed: Dec. 15, 2006 (52) U.S. Cl. ......................................... 424/408; 424/661 (86). PCT No.: PCT/US2006/047729 (57) ABSTRACT S371 (c)(1), A solid composition for forming chlorine dioxide on demand (2), (4) Date: Apr. 28, 2008 and a sealed biocide article. Patent Application Publication Dec. 4, 2008 US 2008/0299161A1 US 2008/02991 6 1 A1 Dec. 4, 2008 SOLD BOCDE COMPOSITION AND 0009. Published US 2005/0249658 B2 describes a solid SEALED BOCDE ARTICLE chlorine dioxide releasing composition having increased temperature stability. The increased temperature stability is provided by using a combination of two chlorine-releasing 0001. This application claims priority to U.S. Provisional agents: Sodium dichloroisocyanurate and a hypochlorite salt. Patent Application Ser. Nos. 60/812,632, filed Jun. 12, 2006 The application also teaches that using an acidulant with a and 60/750,786, filed Dec. 16, 2005, the complete disclosures pKa of 2.8-6.0 further enhances temperature stability. of which are incorporated herein by reference. 0010. A halogen-enhanced oxidizing composition and a solvent activated reactor are described in published applica FIELD OF THE INVENTION tions US 2005/O155936A1 and US 2006/0013751 A1. Solid 0002 The invention relates to a solid biocide composition. oxidizing compositions including chlorine dioxide are The composition rapidly releases chlorine dioxide when con described. The application describes the use of a metal chlo tacted with water or moisture. The invention also relates to a rite, oxidizing agent, and chloride Salt to produce chlorine sealed biocide article. dioxide. (0011 US 2006/0016765 A1 describes a composition for BACKGROUND OF THE INVENTION producing chlorine dioxide comprising an active oxygen compound and a chlorine dioxide-generating compound. See 0003 Chlorine dioxide is a highly reactive yellowish paragraph 23. Preferred active oxygen compounds are Sulfur green gas that produces useful aqueous solutions in a number containing oxy-acid compounds. See paragraph 26. Suitable of applications such as disinfection, Sterilization, and odor precursors for producing chlorine dioxide include chlorite control. It is a potent antimicrobial agent, bleaching agent, salt, alkali metal salt or alkaline earth halide salt. See para and as a germicide has found increasing receptivity of its use graph 26. The preferred composition is sodium chlorite, in municipal and drinking water treatment, cooling towers, potassium monoperSulfate, and magnesium chloride. This and food processing. publication discloses a large list of metal halides, which can 0004 Recent regulatory approvals have led to growing be added as a “catalyst to speed up generation of chlorine acceptance of its use in reducing pathogens in food process dioxide of which zinc bromide is listed. See paragraphs 42. ing applications such as poultry chill water tanks, beef and However, the Zinc bromide was used at a pH of 4.1. SeeTable pork carcasses washes, and raw agricultural commodities. 1. Furthermore, the publication teaches that calcium bromide 0005 Chlorine dioxide has many advantages over tradi at a pH of 3.7 is a "comparative example C, i.e. does not tional chlorine-based biocides due to its greater selectivity work, and it gives an orange color which may interfere with towards bacterial cell membranes. However, several draw results, thus, teaching away from using calcium bromide. See backs have limited the implementation of chlorine dioxide Table 1. Furthermore, this publication does not teach forming where its superior safety and environmental profile would hypobromous acid at a pH of 5-9 or the many advantages benefit a wide variety of industries. thereof. 0012. There is a need for a solid biocide composition that PRIOR ART OF SOLID COMPOSITIONS rapidly produces chlorine dioxide in the presence of water or 0006. The prior art describes methods to produce chlorine moisture on demand, without producing Substantial amounts dioxide from dry compositions such as tablets, powders, and of chlorine gas or other undesired compounds. briquettes. The prior art has been extensively covered in pub lished U.S. patent applin ser. No. 2004/0135116, which is OBJECTS OF THE INVENTION incorporated herein by reference. 0013 The generation of chlorine dioxide from a chlorite 0007 U.S. Pat. No. 6,602,442 describes a “dry composi salt using a weak hypohalous acid with a pKa value of about tion' comprising lithium hypochlorite, sodium chlorite, and 8.6 as the oxidizing species. Sodium hydrogen Sulfate. Although this mixture was found to 0014. The generation of chlorine dioxide from a chlorite very soluble and rapidly yield chlorine dioxide upon addition salt using a weak hypohalous acid with an acidity constant of to water, a Substantial amount of chlorine gas is undesirably 2.3x10. released since chlorine is produced above its solubility in water. See column 2, line 55-56 of this patent. Furthermore, (0015 Generating the ionic species OCl and/or OBr. the stability of the dry mixture is limited, especially in high when the present invention is contacted with water or mois humidity environments. These limitations preclude the addi ture. tion of large amounts to water since the excess chlorine pro 0016 Generating the ionic species HOCl and/or HOBr duction would cause the mixture to “flash'. when the present invention is contacted with water or mois 0008 Published U.S. patent applin ser. No 2004/0135116 ture. and U.S. Pat. No. 6,699,404 describe solid chlorine dioxide 0017. The generation of chlorine dioxide from a chlorite releasing “massive bodies, which comprise a mixture of salt using a weak hypohalous acid with an oxidation capacity granular particulate ingredients where the size of the particles of 1.33 electron volts as the oxidizing species. is substantially smaller than the size of the massive body. The 0018. The generation of hypohalous acid to form chlorine massive body is formed from the mixture of particulate ingre dioxide from a chlorite salt using a monopersulfate oxidizing dients by compression and is essentially a large tablet. The agent with an oxidation capacity of 1.44 electron Volts. tablets release chlorine dioxide and free chlorine when added 0019. The generation of chlorine dioxide at a reaction pH to liquid water. The patent claims a composition of a chlorite from 5.0-9.0 using an oxidizing agent, a chlorite salt, and a salt, an acid source, and free halogen source, with the pre bromide salt. ferred composition being sodium chlorite, sodium bisulfate, 0020. The generation of chlorine dioxide where a liquid and the Sodium salt of dichloroisocyanuric acid. halogen with a deep reddish brown color is formed as an US 2008/02991 6 1 A1 Dec. 4, 2008 intermediate step to formation of chlorine dioxide. The liquid (preferably about 6.5 to about 7.5) compared when using halogen is heavier than water and is found at the bottom of the hypochlorous acid. A rapid and high yield of chlorine dioxide reaction vessel. is released when hypobromous acid is produced in the pres 0021. The generation of chlorine dioxide where a liquid ence of chlorite ions. halogen is formed and has an atomic number of 35. 0039. The unique reaction is clearly visible as a brown 0022. The generation of chlorine dioxide where a bro liquid heavier than water and is formed immediately upon the mine-like odor is formed prior to the characteristic chlorine addition of the composition to water. The brown liquid col dioxide odor. lects on the bottom of the reaction vessel forming a thin layer 0023 The generation of chlorine dioxide where acidulant over the solid composition. The brown liquid is believed to be materials are not required to maintain a pH less than 5.0. the halogen, bromine. As the reaction continues, the charac 0024. A solid biocide composition that does not possess a teristic yellow color of chlorine dioxide is quickly visible and chlorine-like odor. increases until the brown color completely disappears. In less 0025. A solid biocide composition that does not contain a than 5 minutes, the chlorine dioxide solution is a bright yel free halogen releasing compound in the composition. A free low color and has reached its maximum concentration. halogen releasing compound is defined where if added to 0040. This surprisingly enhanced chlorine dioxide releas water it will generate measurable free halogen. ing effect is believed to occur because of the different pKa 0026. A solid biocide composition consisting of only inor values of the two weak acids. Hypobromous acid has a pKa of ganic chemicals or where the carbonatom is not present in the 8.6 compared to a pKa of 7.5 for hypochlorous acid. At a pH formula. of 7.5, less than 50% of the active oxidizing agent HOCl is 0027. The generation of chlorine dioxide using any com present, compared to 94% for HOBr. The hypochlorous acid pound that produces hypobromous acid upon contact with pathway reactions utilized in the prior art require the use of Water Or SeaWater. additional acidulant materials to ensure rapid conversion of 0028. To produce a solid biocide article that is not subject the chlorite ion to chlorine dioxide.
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