WO2021242225A1 - Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability - Google Patents
Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability Download PDFInfo
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- WO2021242225A1 WO2021242225A1 PCT/US2020/034601 US2020034601W WO2021242225A1 WO 2021242225 A1 WO2021242225 A1 WO 2021242225A1 US 2020034601 W US2020034601 W US 2020034601W WO 2021242225 A1 WO2021242225 A1 WO 2021242225A1
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- cio2
- amount
- solution
- dowfax
- chlorine dioxide
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 305
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 152
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title abstract description 18
- 238000009472 formulation Methods 0.000 title description 3
- 239000004615 ingredient Substances 0.000 claims abstract description 17
- 230000007774 longterm Effects 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 129
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 104
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 28
- 229960002218 sodium chlorite Drugs 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 229910001868 water Inorganic materials 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 7
- 239000003599 detergent Substances 0.000 claims description 7
- 239000003205 fragrance Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 5
- 230000007423 decrease Effects 0.000 claims 1
- 239000000645 desinfectant Substances 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 53
- 239000004094 surface-active agent Substances 0.000 description 19
- 229910001919 chlorite Inorganic materials 0.000 description 10
- 229910052619 chlorite group Inorganic materials 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 9
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000012895 dilution Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003139 biocide Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000000249 desinfective effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical class [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 206010013496 Disturbance in attention Diseases 0.000 description 2
- LTGPFZWZZNUIIK-LURJTMIESA-N Lysol Chemical compound NCCCC[C@H](N)CO LTGPFZWZZNUIIK-LURJTMIESA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000011012 sanitization Methods 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000013020 final formulation Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002324 mouth wash Substances 0.000 description 1
- 229940051866 mouthwash Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
Definitions
- the present invention is generally related to broad spectrum disinfectants, sanitizers, cleaners or deodorizers using chlorine dioxide compositions, and more particularly, to methods for producing chlorine dioxide compositions having improved long term stability by the proper choice of pH and through the careful choice of other product formula ingredients.
- CIO2 chlorine dioxide
- hypochlorite peroxide
- quaternary amines quaternary amines
- Chlorine dioxide is an effective biocide and can clean and deodorize.
- CIO2 does not chlorinate organic compounds.
- it is inherently less stable than other biocides such as quaternary amines. Due to instability, most applications involve producing chlorine dioxide at the source of use. Therefore, chlorine dioxide must be properly formulated to be viable.
- a disinfectant or sanitizing or cleaner/deodorizer product that maximizes the stability of the active ingredients so that the product has a suitable shelf-life and is ready to use after manufacturing.
- Stable products have a longer shelf-life, better consumer appeal, and are easier to use.
- a stable product can use conventional package that are readily available and cheaper.
- the invention is a device for delivering stabilized chlorine dioxide having improved long term stability by the proper choice of pH.
- a number of synthesis reactions are known for producing chlorine dioxide.
- the preferred method is the acidification of chlorite.
- the device includes a delivery device configured to deliver a solution to a target application and a stabilized chlorine dioxide (CIO2) product that is configured to be delivered using the delivery device.
- the chlorine dioxide is produced using a method that includes adding a first amount of Hydrochloric acid (HCI) to a second amount of Sodium chlorite (NaCIO2) that is dissolved in water, the first amount being greater than the second amount; agitating the HCL and NaCI02 for at least 10-15 minutes to mix the chemicals and thus allowing the chemical to react to completion; adding a third amount of Dowfax to the solution and slowly agitate the HCI, NaCI02 and Dowfax solution to distribute the Dowfax; and after the reaction to generate chlorine dioxide (CIO2) in solution has gone to completion, adding a fourth amount of Sodium Hydroxide (NaOH) to adjust the pH of the resulting CI02 solution to a desired pH and concentration.
- HCI Hydrochloric acid
- NaCIO2 Sodium chlorite
- the invention is a method of making a high concentration chlorine dioxide with improved long-term stability comprising.
- the method includes adding 42.61 g/l 10% Hydrochloric acid (HCI) to 3.20g/l Sodium chlorite (NaCIO 2 ) dissolved in water; agitating the HCL and NaCIO2 for at least 10-15 minutes to mix the chemicals; adding 1.50g/l of Dowfax and slowly agitate the HCI, NaCI02 and Dowfax solution to distribute the Dowfax; and adding 42.23g/l of 5% Sodium Hydroxide (NaOH) to adjust the pH of the CIO2 solution to a desired pH.
- HCI Hydrochloric acid
- NaCIO 2 Sodium chlorite
- the invention is a method for producing a high concentration chlorine dioxide with improved long-term stability.
- HCI Hydrochlor
- the delivery device is a spray bottle and the stabilized CIO2 is a sprayable solution; the delivery device is a wipe and the stabilized CI02 is a solution integrated into the wipe; the delivery device is a tablet and the stabilized CIO2 is integrated into the tablet; the delivery device delivers a laundry detergent and the stabilized CIO2 is integrated into the laundry detergent; the delivery device delivers a deodorizer and the method of producing the CIO2 further comprises adding a fragrance ingredient compatible with CI02; the delivery device is a cleaning device and the stabilized CIO2 is produced as a concentrate that can be used at full strength or diluted with water.
- the CIO2 concentration is 1200-1300 PPM.
- the CI02 concentration is 1250 PPM
- the CIO2 is: a sprayable solution configured to work with a spray bottle; the CIO2 is a concentrated solution configured to be used at full strength or diluted with water prior to use; the method further comprising adding a fragrance ingredient compatible with CIO2 to produce a fragranced solution.
- Figure 1 shows a stability profile of chlorine dioxide compositions with differing pH levels vs. time.
- Figure 2 shows a stability profile of chlorine dioxide and surfactant compositions with differing pH levels vs. time.
- Figure 3 shows a stability profile of chlorine dioxide and surfactant compositions with differing pH levels vs. time.
- Figure 4 shows a stability profile for a series of samples with Dowfax
- Figure 5 shows a plot of the percent of CIO2 remaining as a function of pH.
- the present invention is directed to improve the stability of chlorine dioxide (CIO2) compositions and products.
- CIO2 chlorine dioxide
- the inventor has found that the stability of the chlorine dioxide can be significantly improved by the proper choice of pH, and through the careful choice of other product formula ingredients.
- the product has a suitable shelf-life and is ready to use after manufacturing. This stabilization benefit applies regardless of the reaction method used to produce chlorine dioxide.
- the improved stability of CIO2 is due to adjusting the pH.
- the relationship between pH and stability may not be recognized, and that could explain the limited number of CIO2 based product in the market.
- the increased stability of CIO2 would make a product more desirable than a similar product with limited shelf-life, or a product that must be mixed prior to use.
- Chlorine dioxide can be produced by a number of reactions with sodium chlorite (NaCIO2).
- NaCIO2 sodium chlorite
- Several industrial methods of synthesis of chlorine dioxide are known such as acidification of chlorite, oxidation of chlorite by chlorine, oxidation of chlorite by persulfate.
- Other suitable reactions include the reaction of acetic anhydride with chlorite, the reduction of chlorates by acidification in the presence of oxalic acid, and the reduction of chlorates by sulfurous anhydride.
- Acidification of chlorite according to the following reaction is particularly appealing due to the availability, cost and ease of use of hydrochloric acid. It is understood that regardless of the method used to produce chlorine dioxide, the stability of the solution is controlled by pH and the proper choice of other ingredients.
- Any suitable acid may be used in the process disclosed.
- hydrochloric acid sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, sulfamic acid, succinic acid, and oxalic acid.
- Acids may be moderate to strong acids that are capable of reacting with sodium chlorite to form CIO2.
- the strongest acids are “mineral acids.” Common examples are hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid. These are characterized as having pKa values ⁇ 1. Strong acids react very quickly with sodium chlorite.
- Moderately strong acids include many organic acids. Examples include acetic acid, citric acid, sulfamic acid, succinic acid, and oxalic acid. These are characterized as having pKa values pKa about 5. The acid needs to react with sodium chlorite to form CIO2. If the pka is too high, the reaction will not occur or will be very slow. The lower the pKa, the stronger the acid and the faster the reaction with sodium chlorite.
- the process may also include a caustic, such as sodium hydroxide to adjust the solution pH
- NaCI02 sodium chlorite
- HCI hydrochloric acid
- a first batch of CIO2 (3-134), prepared as described in Formula (1 ) was split into two subsamples.
- the pH of one subsample was adjusted to pH 3.66 with Sodium Hydroxide (NaOH) (3-134A) and the other subsample was not adjusted and was pH 1.70 (3-134B).
- the pH of one subsample was adjusted to pH 3.62 (3-131 A) and the second subsample was not adjusted and was pH 1.96 (3-131 B).
- the samples were stored in closed amber glass jars. At various times, aliquots were removed and the CI02 was assayed using the iodometric titration.
- Figure 1 is a plot of the CIO2 concentration vs. time for the samples. As seen in the plot, increasing the pH results in a much more stable product, i.e. slower loss of the CI02 concentration over time. Raising the sample pH also has the key benefit of preventing the initial rapid drop in CIO2 typically seen in the first few days after synthesis of CIO2. Preventing this initial drop in activity is more cost effective for manufacturing and makes it easier to achieve the desired concentration.
- Figure 2 shows a stability profile of another set of samples with surfactant added (3-142), in this case, Dowfax 3B2 surfactant.
- the CIO2 (3-142) was prepared as described in Formula (1) and split into two subsamples. The pH of one subsample was adjusted to pH 3.64 (3-142B) with Sodium Hydroxide (NaOH) and the other subsample was not adjusted and was pH 1.73 (3-134A). Both samples were stored in closed amber glass jars. At various times, aliquots were removed and the CIO2 was assayed using the iodometric titration.
- Figure 2 is a plot of the CIO2 concentration with vs. time. This plot again shows increasing the pH to 3.64 results in a much more stable product than the pH 1.73 sample, i.e. slower loss of the CIO2 concentration over time.
- Figure 3 shows a stability profile of another set of samples with surfactant added (3-170), in this case, Dowfax 3B2 surfactant.
- Figure 3 is similar Figure 2 but with samples at a broader range in pH.
- the CIO2 with surfactant was prepared as described and split into seven subsamples.
- the pH of the first subsample 3-170A was not adjusted and was pH 1 .76.
- the pH of the other subsamples 3-170B to 3-170G were adjusted with Sodium Hydroxide (NaOH). All samples were stored in closed amber glass bottles.
- NaOH Sodium Hydroxide
- 3-170 A pH 1.76 3-170B adjusted to pH 2.34 3-170C adjusted to pH 3.00 3-170D adjusted to pH 3.64 3-170E adjusted to pH 4.17 3-170F adjusted to pH 4.97 3-170G adjusted to pH 7.18
- FIG. 3 shows the effect of pH on stability.
- the graph shows raising the pH in subsamples 3-170B to 3-170G improved stability.
- sample 3-170G with pH 7.18 was not as stable as the samples as pH 4.97 (3-170F), suggesting there may be an optimal pH range for stability where pH ⁇ 5 appears to have better stability than pH 3.6.
- Figure 4 shows the stability profile for yet another series of samples with Dowfax 3B2 (Sample series 3-176A-J). The same procedure was used in preparing the samples. A large sample batch was prepared which was then split into ten sub samples. The pH of the subsamples was adjusted by addition of sodium hydroxide. The samples were stored at room temperature in closed amber glass bottles. At various times, aliquates from the subsamples were removed and the concentration of CIO2 was assayed using an iodometric titration. The sample pH’s were checked and adjusted if necessary to the original sample pH. The initial concentration of CIO2 was 545 PPM. Table A shows the concentration of CIO2 and the corresponding calculated percent remaining based on the initial concentration at 6, 14 and 37 weeks.
- Table 1 shows a base solution composition used for disinfectant/sanitizer solution depicted in Figure 1 3-134 A/B.
- NaCIO2 is dissolved in deionized water.
- the aliquot of 10% HCI was added.
- the mixture is stirred and allowed to react for 15 minutes.
- the batch was then split into two 11 subsamples.
- Chlorine dioxide decomposes more quickly when exposed to light, is temperature sensitive and it reacts with many organic compounds. Proper shielding from light and clean production facilities and handling procedures, and material purity are essential to improve stability and avoid unwanted reactions with organic contaminants during production.
- the resulting concentration of chlorine dioxide can be tailored to meet the desired biocidal performance.
- the product of the concentration and the contact time l.e. c x t constant.
- doubling the concentration can result in a reduction of concentration to yield a similar degree of micro efficacy.
- Table 3 shows typical ranges of ingredients to produce sanitizer/disinfecting/deodorizing solutions.
- the examples described above had a starting concentration of about 550 PPM CIO2.
- the present invention also contemplates making a solution of chlorine dioxide with higher concentration 1200-1300 PPM having a pH 4.5-6.5 for various applications.
- the upper limit of HCI assumes a several fold molar excess of HCI to speed the reaction rate.
- Table 4 shows an example of ingredients for producing a product having about 1250 PPM CI02 and Ph 5.91.
- a batch of the 1250 PPM CIO2 was prepared as described in Table 4 and was split into two subsamples. The pH of one subsample was not adjusted and was pH 1.50 and the second subsample adjusted using 42.3 gm of 5% NaOH to a pH 5.91 .
- the production/manufacturing for the CIO2 based solution should follow general manufacturing guidelines that are typically followed in the production of hypochlorite or peroxide containing based products. All contact surfaces in the production equipment, filling and line and packaging should be in good condition. They must/should be emptied and thoroughly rinsed so as to prevent cross contamination prior to use. Such practices are generally followed in the production of hypochlorite containing products or other products where contamination is undesirable/not tolerated.
- the entire production process for the solution would be conducted under clean room conditions, in order to minimize the possibility of contamination of the solution by environmental contaminants, such as airborne particles.
- All contact surfaces including without limitation surfaces of production equipment, filling equipment and packaging, should be thoroughly cleaned of contaminants prior to use.
- Deionized water should be used to prepare or dilute the Solution during production of the finished product.
- the pH of the finished product should be adjusted to improve stability and/or to achieve the desired product pH. If the product is required to have a specific pH, the overall stability of the CI02 could subsequently be affected. It is therefore preferred to have the product pH fall within the range of pHs that promotes the improved stability.
- Surfactant and other adjuncts can be added to the basic solution to create a range of products.
- Surfactants such as Dowfax 3B2 help facilitate cleaning and wetting of surfaces to improve the micro efficacy of chlorine dioxide.
- Gum thickeners can be added to thicken the product to improve contact time on a vertical surface or potentially as in a hand sanitizer.
- gum thickeners may include, but not limited to, xanthan gum, Kelzan AP-AS (from CP Kelco), Keltrol (from CP Kelco) or other suitable gum thickener.
- the key is that the adjuncts must be reasonably stable with chlorine dioxide.
- the benefits of proper pH choice also apply to the addition of adjuncts. We are not limited to just these two ingredients. Optimizing the pH will improve stability of formula containing the desired adjuncts.
- a concentrated product could have applications such as a floor cleaner, general cleaner/deodorizer, use in toilet bowl, or in laundry applications.
- the concentrated product is a product that may be used full strength or be diluted prior to use.
- the product is prepared using a stabilized formula and then diluted by adding additional water or adding the concentrated formula to water.
- An example of a concentrated product and how one is used, is Pine -Sol. You can use Pine -Sol full strength or dilute it. The standard calculations would apply in terms of dilutions i.e. add product to an equal amount of water would dilute it by 50% etc.
- the concentrate could be a refill for a spray product.
- the concentration of the chlorine dioxide and the surfactant would be higher in the concentrated product to allow for dilution so that the diluted product will still have ingredients to be effective.
- Higher concentration of CIO2 may be used to sanitize or disinfect while a lower concentration of CIO2 in the diluted form may be good for general cleaning and deodorizing.
- the concentrated product should be safe to use and have a suitable shelf life for storage.
- the product may include other ingredients, such as fragrance, dyes, or thickeners, etc to change the aesthetics or the form of the product or even change other performance attributes.
- gum may he added to make a gel product.
- CIO2 product disclosed herein may be used in many different products depending on the final dilution and concentration. Uses may include sanitizer or disinfectant, floor cleaner, general cleaner/deodorizer, use in toilets, mouthwash or in laundry applications. The product may be used along or combined with other products.
- CIO2 product be delivered in many different forms, depending on the application. Below are some non-limiting examples.
- the CIO2 product may use many different delivery devices depending on the application.
- the CIO2 product may be packaged in a spray bottle or package of wipes.
- the CIO2 product be in a squirt bottle,
- Floor Cleaner - The CI02 product may be provided in a con centrated solution that can be used either at full concentration or diluted, such as Pine-Sol.
- the CIO2 product may be provided in a spray bottle, like Lysol, or disinfecting wipes like Clorox Wipes.
- Toilet - The CIO2 product m ay be provided in a tablet form to drop-in the bowl or put in the toilet tank for each flush, like Clorox tablets.
- the tables may be different concentration, such as the drop-in bowl tablet may have a higher concentration than the tank tablet.
- Laundry - The CIO2 product may be mixes in a laundry detergent, or may be a separate solution additive, like Lysol Laundry Sanitizer Additive, or as beads that are thrown in the wash, like Downy Fresh Scent Booster Beads
- the present invention is directed to improve the stability of chlorine dioxide (CIO2) compositions and products by the proper choice of pH, and through the careful choice of other product formula ingredients.
- CIO2 chlorine dioxide
- the product has a suitable shelf-life and is ready to use after manufacturing.
- the device includes a delivery device configured to deliver a solution to a target application and a stabilized chlorine dioxide (CIO2) product that is configured to be delivered using the delivery device.
- the chlorine dioxide is produced using a method that includes adding a first amount of Hydrochloric acid (HCI) to a second amount of Sodium chlorite (NaCIO2) that is dissolved in water, the first amount being greater than the second amount; agitating the HCL and NaCIO2 for at least 10-15 minutes to mix the chemicals and thus allowing the chemical to react to completion; adding a third amount of Dowfax to the solution and slowly agitate the HCI, NaCIO2 and Dowfax solution to distribute the Dowfax; and after the reaction to generate chlorine dioxide (CIO2) in solution has gone to completion, adding a fourth amount of Sodium Hydroxide (NaOH) to adjust the pH of the resulting CIO2 solution to a desired pH and concentration.
- HCI Hydrochloric acid
- NaCIO2 Sodium chlorite
- the invention is a method of making a high concentration chlorine dioxide with improved long-term stability comprising.
- the method includes adding 42.61 g/l 10% Hydrochloric acid (HCI) to 3.20g/l Sodium chlorite (NaCIO2) dissolved in water; agitating the HCL and NaCIO2 for at least 10-15 minutes to mix the chemicals; adding 1.50g/l of Dowfax and slowly agitate the HCI, NaCIO2 and Dowfax solution to distribute the Dowfax; and adding 42.23g/l of 5% Sodium Hydroxide (NaOH) to adjust the pH of the CIO2 solution to a desired pH.
- HCI Hydrochloric acid
- NaCIO2 Sodium chlorite
- the invention is a method for producing a high concentration chlorine dioxide with improved long-term stability.
- HCI Hydrochloric
- the delivery device is a spray bottle and the stabilized CIO2 is a sprayable solution; the delivery device is a wipe and the stabilized CIO2 is a solution integrated into the wipe; the delivery device is a tablet and the stabilized CIO2 is integrated into the tablet; the delivery device delivers a laundry detergent and the stabilized CIO2 is integrated into the laundry detergent; the delivery device delivers a deodorizer and the method of producing the CIO2 further comprises adding a fragrance ingredient compatible with CIO2; the delivery device is a cleaning device and the stabilized CIO2 is produced as a concentrate that can be used at full strength or diluted with water.
- the desired pH is 4.5 - 6.5, and in other embodiments the desired pH is 5.91 .
- the CIO2 is: a sprayable solution configured to work with a spray bottle; the CIO2 is a concentrated solution configured to be used at full strength or diluted with water prior to use; the method further comprising adding a fragrance ingredient compatible with CIO2 to produce a fragranced solution.
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CA3185170A CA3185170A1 (en) | 2020-05-26 | 2020-05-26 | Devices, systems, and methods of making and using chlorine dioxide based formulation with improved stability |
PCT/US2020/034601 WO2021242225A1 (en) | 2020-05-26 | 2020-05-26 | Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability |
EP20937200.2A EP4157497A4 (en) | 2020-05-26 | 2020-05-26 | Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability |
AU2020450618A AU2020450618A1 (en) | 2020-05-26 | 2020-05-26 | Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability |
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PCT/US2020/034601 WO2021242225A1 (en) | 2020-05-26 | 2020-05-26 | Devices, systems and methods of making and using chlorine dioxide based formulation with improved stability |
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EP (1) | EP4157497A4 (en) |
AU (1) | AU2020450618A1 (en) |
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Citations (4)
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CN1196881A (en) * | 1997-04-21 | 1998-10-28 | 上海文华消毒药业科技有限公司 | High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. |
US20070202095A1 (en) * | 2006-02-28 | 2007-08-30 | Speronello Barry K | Chlorine dioxide based cleaner/sanitizer |
US20120207858A1 (en) * | 2011-02-14 | 2012-08-16 | Truox, Inc. | Biocide and bleach compositions and related methods |
US20150237864A1 (en) * | 2014-02-26 | 2015-08-27 | Disinfection Research Llc | Broad spectrum disinfectant |
Family Cites Families (1)
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US10660339B2 (en) * | 2018-06-04 | 2020-05-26 | Spectrum Doxyicide, Llc | Chlorine dioxide based formulation with improved stability |
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2020
- 2020-05-26 CA CA3185170A patent/CA3185170A1/en active Pending
- 2020-05-26 WO PCT/US2020/034601 patent/WO2021242225A1/en unknown
- 2020-05-26 EP EP20937200.2A patent/EP4157497A4/en active Pending
- 2020-05-26 AU AU2020450618A patent/AU2020450618A1/en active Pending
Patent Citations (4)
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CN1196881A (en) * | 1997-04-21 | 1998-10-28 | 上海文华消毒药业科技有限公司 | High concentration stable chlorine dioxide solid sterilizing tablets and its prepn. |
US20070202095A1 (en) * | 2006-02-28 | 2007-08-30 | Speronello Barry K | Chlorine dioxide based cleaner/sanitizer |
US20120207858A1 (en) * | 2011-02-14 | 2012-08-16 | Truox, Inc. | Biocide and bleach compositions and related methods |
US20150237864A1 (en) * | 2014-02-26 | 2015-08-27 | Disinfection Research Llc | Broad spectrum disinfectant |
Non-Patent Citations (3)
Title |
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ANONYMOUS: "DOWFAX 3B2 Solution Surfactant", DOW, 28 August 2020 (2020-08-28), XP055880886, Retrieved from the Internet <URL:https://www.dow.com/en-us/pdp.dowfax-3b2-solution-surfactant.23261z.html> * |
ANONYMOUS: "Rate equation", 1 January 1997 (1997-01-01), pages 1 - 17, XP093012575, Retrieved from the Internet <URL:https://en.wikipedia.org/wiki/Rate_equation> [retrieved on 20200831] * |
See also references of EP4157497A4 * |
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EP4157497A4 (en) | 2024-02-21 |
EP4157497A1 (en) | 2023-04-05 |
AU2020450618A1 (en) | 2023-02-02 |
CA3185170A1 (en) | 2021-12-02 |
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