Patent Grant
8951576
The present invention relates to a process for producing an aqueous chlorous acid solution used for disinfection/sterilization of food for pretreatment in food processing operations and related facilities.
Conventionally, chlorine oxides (e.g., chlorine, hypochlorous acid, chlorous acid, and chlorine dioxide) are primarily used for disinfection or sterilization of food for pretreatment in food processing operations, such as fresh perishable food including vegetables and fruits, and the facilities related to processing and production of processed food, such as containers, preparation/cooking machinery, and plant equipment. Of these, chlorine and hypochlorous acid, when reacted with organic compounds, are known to produce trihalomethanes, which are carcinogenic compounds. This, along with recent health-consciousness trend, has focused attention on acidified sodium chlorite (ASC) solution, which was developed in the United States of America and which possesses a high bactericidal effect and is less associated with trihalomethane-related adverse effects. Reference 1: U.S. Pat. No. 6,524,624
To produce the above-mentioned ASC solution, an aqueous chlorous acid solution is mixed with an acid known as “generally recognized as safe” (GRAS) and adjusted to pH 2.3 to 3.2.
However, the main active component of the above-mentioned ASC solution, chlorous acid, decomposes a short time after preparation due to its low stability, thereby reducing its bactericidal potential. The above-mentioned ASC solution, therefore, needs to be prepared immediately before use.
This preparation procedure is not only inconvenient but also associated with the disadvantages resulting from production of chlorine dioxide gas, which is highly likely to have toxic effects on individuals who inhale it and corrosive effects on food-processing and cooking machinery and other related equipment.
The present invention was made taking into account the above disadvantages. The purpose of the present invention is to provide an easy-to-handle, long-acting, stable aqueous chlorous acid solution. Another purpose of the present invention is to provide a disinfectant for use in pretreatment of food-processing operations that releases a reduced amount of chlorine dioxide, is safe to human health, and possesses a high bactericidal activity.
In order to solve the aforementioned problems, a first feature of the process of the present invention is to employ a process for producing an aqueous chlorous acid solution for use as disinfectant, comprising: reacting an aqueous sodium chlorate solution with a volume and concentration of sulfuric acid or aqueous solution thereof appropriate for maintaining pH of said aqueous solution at 2.3 to 3.4, thereby generating chloric acid, and subsequently adding thereto at least an amount of hydrogen peroxide required for reducing said chloric acid to produce chlorous acid.
A second feature of the process of the present invention is to employ a process for producing an aqueous chlorous acid solution for use as disinfectant, comprising: reacting an aqueous sodium chlorate solution with a volume and concentration of sulfuric acid or aqueous solution thereof appropriate for maintaining pH of said aqueous solution at 2.3 to 3.4, thereby generating chloric acid, subsequently adding thereto at least an amount of hydrogen peroxide required for reducing said chloric acid to produce chlorous acid, and adding to the resulting aqueous solution at least one compound selected from the group consisting of inorganic acids and salts or a combination thereof, to adjust its pH in the range of 3.2 to 7.0.
A third feature of the process of the present invention is to employ a process for producing an aqueous chlorous acid solution for use as disinfectant, comprising: reacting an aqueous sodium chlorate solution with a volume and concentration of sulfuric acid or aqueous solution thereof appropriate for maintaining pH of said aqueous solution at 2.3 to 3.4, thereby generating chloric acid, subsequently adding thereto at least an amount of hydrogen peroxide required for reducing said chloric acid to produce chlorous acid, and adding to the resulting aqueous solution at least one compound selected from the group consisting of inorganic and organic acids and salts or a combination thereof, to adjust its pH in the range of 3.2 to 7.0.
A forth feature of the process of the present invention is to employ a process for producing an aqueous chlorous acid solution for use as disinfectant, comprising: reacting an aqueous sodium chlorate solution with a volume and concentration of sulfuric acid or aqueous solution thereof appropriate for maintaining pH of said aqueous solution at 2.3 to 3.4, thereby generating chloric acid, subsequently adding thereto at least an amount of hydrogen peroxide required for reducing said chloric acid to produce chlorous acid, adding to the resulting aqueous solution at least one compound selected from the group consisting of inorganic acids and salts or a combination thereof, and further adding at least one compound selected from the group consisting of inorganic and organic acids and salts or a combination thereof, to adjust the pH in the range of 3.2 to 7.0.
A fifth feature of the process of the present invention is to employ the process for producing an aqueous chlorous acid solution for use as disinfectant, wherein said inorganic acid according to any of second to forth features of the present process, include carbonic acid, phosphoric acid, boric acid, or sulfuric acid.
A sixth feature of the process of the present invention is to employ the process for producing an aqueous chlorous acid solution for use as disinfectant, wherein said inorganic salts according to any of second to fifth features of the present process include carbonates, hydroxides, phosphates, or borates.
A seventh feature of the process of the present invention is to employ the process for the process for producing an aqueous chlorous acid solution for use as disinfectant, wherein said carbonates according to the sixth feature of the present process include sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate.
A eighth feature of the process of the present invention is to employ the process for the process for producing an aqueous chlorous acid solution for use as disinfectant, wherein said hydroxides according to the sixth or the seventh feature include sodium hydroxide or potassium hydroxide.
A ninth feature of the process of the present invention is to employ the process for producing an aqueous chlorous acid solution for use as disinfectant, wherein said phosphates according to any one of sixth to eight features include disodium hydrogenphosphate, sodium dihydrogenphosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogenphosphate, or potassium dihydrogenphosphate.
A tenth feature of the process of the present invention is to employ the process for producing an aqueous chlorous acid solution for use as disinfectant, wherein said borates according to any one of sixth to ninth features include sodium borate or potassium borate.
A eleventh feature of the process of the present invention is to employ the process for producing an aqueous chlorous acid solution for use as disinfectant, wherein said organic acids according to any one of third to tenth features include succinic acid, citric acid, malic acid, acetic acid, or lactic acid.
A twelfth feature of the process of the present invention is to employ the process for producing an aqueous chlorous acid solution for use as disinfectant, wherein said organic salts according to any one of third to eleventh features include sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, or calcium lactate
According to the present invention, there can be provided an aqueous chlorous acid solution which is highly disinfectant and stable, so that it will not need to be prepared immediately before being used and it is made possible to be preserved for future use. In addition, it prevents generation of chlorine dioxide so as to be harmless to human body and can be used without anxiety.
Moreover, the aqueous chlorous acid solution produced in accordance with the present invention can maintain prolonged stability and can be marketed as disinfectant commodities.
Hereinafter, the preferred embodiments of the present invention will be described with reference to accompanying figures and tables.
Example 1 of the present invention provides a process for producing an aqueous chlorous acid (HClO2) solution for use as disinfectant. According to this process, sulfuric acid (H2SO4) or aqueous solution thereof is added to an aqueous sodium chlorate (NaClO3) solution to create acidic conditions, thereby generating chloric acid (HClO3), and the resulting chloric acid undergoes a reduction reaction with an excess amount of hydrogen peroxide to produce chlorous acid (HClO2). The essential chemical reactions of this production process are presented by the following equations A and B:
[Chemical Formula 1]
2NaClO3+H2SO4→2HClO3+Na2SO4↓ (Equation A)
HClO3+H2O2→HClO2+H2O+O2↑ (Equation B)
Equation A indicates that chloric acid is generated by addition of an amount and concentration of sulfuric acid (H2SO4) or aqueous solution thereof appropriate for maintaining the pH of the aqueous sodium chlorate (NaClO3) solution at 2.3 to 3.4, while sodium ions are eliminated concurrently.
Then, equation B shows that chloric acid (HClO3) undergoes a reduction reaction with hydrogen peroxide (H2O2) to produce chlorous acid (HClO2). This reaction requires the addition of at least an amount of hydrogen peroxide (or aqueous solution thereof) stoichiometrically required for the reduction reaction. Otherwise, the reaction will yield only chlorine dioxide.
[Chemical Formula 2]
HClO3+H2O2→2ClO2+H2O+O2↑ (Equation C)
2ClO2+H2O2→2HClO2+O2↑ (Equation D)
2ClO2+H2OHClO2+HClO3 (Equation E)
2HClO2H2O+Cl2O3 (Equation F)
In cases where chlorine dioxide is generated, it will be converted to chlorous acid by a series of reactions shown by equations C to F.
Chlorous acid (HClO2) thus produced possesses the propensity to decompose quickly to chlorine dioxide gas or chlorine gas by interactions among a plurality of chlorous acid molecules or by the presence of chloride (Cl−) ions, hypochlorous acid (HClO), or other reductive agents. It is, therefore, necessary to provide a long-acting chlorous acid (HClO2) preparation effective for use as disinfectant.
Under these circumstances, it is necessary to provide a process for producing a stable, long-acting aqueous chlorous acid (HClO2) solution; and this is achieved by creating a transitional state to delay the progress of the decomposition reaction through the addition of at least one compound selected from the group consisting of inorganic and organic acids and salts or a combination thereof, to the aqueous chlorous acid (HClO2) solution produced according to the process described in Example 1 above. This process is embodied in Examples 2, 3, and 4.
Specifically, according to Example 2, the aqueous chlorous acid (HClO2) solution produced according to the process described in Example 1 is mixed with inorganic acid(s) or organic salt(s), or more specifically, at least one compound selected from the group consisting of carbonates and hydroxides or a combination thereof.
Also, according to Example 3, the aqueous solution produced in Example 2 is mixed with at least one compound selected from the group consisting of inorganic and organic acids and salts or a combination thereof.
Moreover, according to Example 4, the aqueous solution produced in Example 1 is mixed with at least one compound selected from the group consisting of inorganic and organic acids and salts or a combination thereof.
As for the above, inorganic acids can be mentioned as well as carbonic acid, phosphoric acid, boric acid, and sulfuric acid. For the inorganic salts, carbonates and hydroxides can be mentioned as well as phosphates and borates. More specifically, the carbonates include sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; the hydroxides include sodium hydroxide and potassium hydroxide; the phosphates include disodium hydrogenphosphate, sodium dihydrogenphosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogenphosphate, and potassium dihydrogenphosphate; and the borates include sodium borate and potassium borate. Moreover, the above organic acids include succinic acid, citric acid, malic acid, acetic acid, and lactic acid; and appropriate examples of the organic salts include sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, and calcium lactate.
In Examples 2, 3, and 4, the following transitional states are temporarily created:
Na++ClO2−⇄Na—ClO2,
K++ClO2−⇄K—ClO2,
H++ClO2−⇄H—ClO2.
These states contribute to delaying the progress of the conversion of chlorous acid (HClO2) to chlorine dioxide (ClO2), which enables the formation of an aqueous chlorous acid solution that is capable of sustaining chlorous acid (HClO2) for an extended time and releases a reduced amount of chlorine dioxide (ClO2).
Now, the lower the pH value (the stronger the acidity) of a chlorine oxide, the stronger its bactericidal potential is known to be. The tables below show the results of experiments on the relationship between pH values and bactericidal powers. In these experiments, a pathogenic Escherichia coli strain (O157:H7) was used as the test microbe. Sodium chlorite (Wako Pure Chemical Industries, Ltd., Osaka, Japan, 80%) was used as the test chlorine oxide. Citric acid (Wako, 98%), lactic acid (Wako, 85% to 92%), and acetic acid (Wako, 99.7%) were used as an activator. Thirty-mL aliquots of an aqueous sodium chlorite solution (0.5 g/L, pH 9.8) were adjusted to pH 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, and 8.0 by addition of citric acid, lactic acid, or acetic acid. Phenol index measurement procedure was employed for assessment of the bactericidal effect. Ten-mL aliquots of the test solutions diluted as appropriate were transferred to test tubes, allowed to warm for at least 5 minutes in a thermostatic water bath set at 20° C.±1° C. Then, 1-mL aliquots of the test microbe preparation, pre-warmed in a similar manner, were added to the test tubes, and sampling was performed by use of a platinum loop at 2.5, 5, 10, and 15 minutes after the addition. The sampled microbial mixtures were inoculated into a normal bouillon medium and incubated at 37° C. for 48 hours. Bacterial growth was visually observed; positive growth was designated as ‘+’ and negative growth as ‘−.’
As shown in the tables above, aqueous sodium chlorite solutions having pH 7.0 or higher fell short of completely eradicating the test E. coli strain in 15 minutes. However, complete eradication was achieved in 2.5 minutes when the pH was adjusted to 4.0 or lower, in 10 minutes when the pH was adjusted to 5.0, and in 15 minutes when the pH was adjusted to 6.0. These findings demonstrate a higher bactericidal potential for sodium chlorite solution having a more acidic pH value. These findings also demonstrate that the difference in the type of activator poses no significant difference in the bactericidal power of sodium chlorite solution.
Thus, chlorite solution exhibits a stronger bactericidal effect when it is more acidic. However, when its pH is strongly acidic, for example, at a value in the order of 2.0, its applicable areas in food industry are limited because of its negative effects such as denaturation of protein components of the sterilized food items.
[Chemical Formula 3]
5ClO2−+4H+→4ClO2+5Cl−+2H2O (5NaClO2+4CH3COOH→4ClO2+4CH3COONa+NaCl+2H2O) (a)
3ClO2−→2ClO3−+Cl−(3NaClO2→2NaClO3+NaCl) Autodecomposition (b)
ClO2−→Cl−+2O (c)
The above Chemical Formula 3 represents the decomposition of chlorite compounds in an acidic solution. When the solution has a lower (more acidic) pH value, the decomposition of chlorite compounds is enhanced, that is, the absolute kinetic rates of the reactions represented by above equations (a), (b), and (c) become elevated. Practically, with a decreased pH value, the dominance of the reaction products of equation (a) is reduced. However, with a decrease in pH, the total decomposition percentage shifts to a larger value, resulting in an increased amount of ClO2 (chlorine dioxide) generated. Therefore, the lower the pH value of the aqueous solution becomes, the more likely it makes the disinfectant harmful to human health and disinfection operation awkward due to the release of toxic and irritating ClO2 gas, although it improves the bactericidal and bleaching potentials. Also, a lower pH solution renders chlorous acid more unstable, and thereby enhances the conversion of chlorous acid to chlorine dioxide. As a result, the duration of the bactericidal activity is reduced.
Therefore, when an aqueous chlorous acid (HClO2) solution is mixed with any of the above-mentioned inorganic acids, inorganic salts, organic acids, or organic salts, the solution should be adjusted to pH 3.2 to 7.0, from the viewpoint of suppressing chlorine dioxide release and maintaining the bactericidal activity. The pH values should reach as high as allowed by the requirements on the bactericidal activity conditions within the above range. This contributes to producing an aqueous chlorous acid solution emitting a reduced amount of chlorine dioxide (ClO2) by slowing the conversion of chlorous acid to sodium chlorite (NaClO2) while maintaining chlorous acid (HClO2) for an extended time.
As described below, to confirm the effects of the present invention, the following samples were prepared and subjected to measurement.
First, a chlorous acid solution prepared according to Example 1 was mixed with 1 mol/L sodium carbonate to pH 5.7. The solution (corresponding to an aqueous chlorous acid solution prepared according to Example 2) was added to a 0.05 mol/L sodium borate/succinate buffer (pH 5.7) to give a 3% chlorous acid content. To sum up, this solution (corresponding to an aqueous chlorous acid solution prepared according to Example 3) was prepared by adding to an aqueous chlorous acid solution an inorganic salt compound, followed by addition of a combination of an inorganic salt and an organic salt as buffer. This solution was termed sample A.
Second, the chlorous acid solution prepared according to Example 1 was mixed with 1 mol/L sodium carbonate to pH 5.7. Subsequently, this solution was mixed with deionized water to give a 3% chlorous acid content. In other words, this solution (corresponding to an aqueous chlorous acid solution prepared according to Example 2) was prepared by adding to an aqueous chlorous acid solution an inorganic salt compound. This solution was termed sample B.
Moreover, an aqueous solution containing 25.0% chlorous acid (Wako, 80%) was mixed with 1 mol/L solution of citric acid (Wako, 98%) to pH 2.6. The resulting solution was mixed with deionized water to give a 3% chlorous acid content. This process corresponds to a conventional technique for preparing above-mentioned ASC solution. This solution was termed sample C.
Furthermore, the chlorous acid solution prepared according to Example 1 was added to 0.05 mol/L sodium borate/succinate buffer (pH 6.8) to give a final pH of 5.7 and a chlorous acid content of 3%. In other words, this solution (corresponding to an aqueous chlorous acid solution prepared according to Example 4) was prepared by adding to an aqueous chlorous acid solution a combination of an inorganic salt and an organic salt as buffer. This solution was termed sample D.
The time-course stability of chlorous acid (HClO2) in each sample was compared by measurement of UV spectra and molecular content. The measurement samples all contained 3% chlorous acid (HClO2). UV spectrum measurement was conducted on a spectrophotometer adjusted to provide an absorbance of approximately 1 at the wavelength of maximum absorption when used to measure sample solutions diluted with an appropriate volume of ion exchanged water. Measurement of chlorous acid content was performed by the iodometric titration method described hereafter. Samples were aerated in an airtight container to eliminate chlorine dioxide dissolved in the samples. Then, approximately 10 g of each sample was measured accurately, and water was added to make the volume precisely 100 mL. These solutions were designated as test solutions. A volume of each of the test solutions containing approximately 0.06 g of chlorous acid (HClO2) was accurately measured, placed in an iodine flask, mixed with 12 mL of sulfuric acid (3→100), and water was added to make the volume approximately 55 mL. Immediately after adding 4 g of potassium iodide to the solution, the flask was stoppered and kept in a dark place for 15 minutes. Titration was performed by using 0.1 mol/L sodium thiosulfate and a starch indicator, and the amount of chlorous acid in the solution was determined by the formula: 1 mL of 0.1 mol/L sodium thiosulfate solution=0.001711 g of HClO2. Separately, blank tests were conducted for correction. The test solutions were stored in a dark place for preservation tests. Aliquots of the test solutions were subjected to measurements of chlorous acid content, UV absorption, and pH values immediately after preparation and at 1, 2, 3, 24, 48, 72, 96, 120, 240, 480, and 720 hours after preparation.
Consequently, the spectrometric measurement results identified two absorption peaks in the wavelength range of 248 to 420 nm immediately after preparation of samples A, B, C, and D: one absorption peak in the vicinity of 260 nm corresponding to acidic chlorite ions (H++ClO2−) and the other absorption peak near 350 nm corresponding to chlorine dioxide (ClO2). These results demonstrate the presence of chlorous acid (HClO2) (
[Chemical Formula 4]
Chain of reactions of chlorous acid, chlorine dioxide, and acidic chlorite ion
For sample C, although the presence of two peaks was clearly recognizable at 1 hour (
Meanwhile, samples A, B, and D showed two peaks near 260 and 350 nm after 30 days (
Of these, sample B, as shown in
Table 4 depicts the changes over time in chlorous acid content. The results show that sample C (ASC) lost half of the initial chlorous acid content within 2 hours after preparation, and lost it almost completely on day 4. On the other hand, samples A, B, and D retained much of the initial chlorous acid content even on day 30. Therefore, the aqueous chlorous acid solutions of the present invention are superior to conventional disinfectants, because they maintain chlorous acid content for an extended time.
Of these, samples A and D maintained the initial chlorous acid content (prepared on day 0) for 30 days. This indicates that the aqueous chlorous acid solutions prepared according to Examples 3 and 4 possess the highest capacities of maintaining the stability of chlorous acid over time.
Lower figures in each cell represent HClO2 content (%), and upper signs designate UV measurement results: +, presence of two absorption peaks identified at 260 and 350 nm; −, presence of a maximum absorption peak identified only in the vicinity of 350 nm.
As can be seen from the above, the aqueous solution obtained by acidifying an aqueous sodium chlorite solution, as in the process for producing ASC, rapidly loses the chlorous acid (HClO2) content by a highly accelerated conversion of the acid to chlorine dioxide (ClO2). The aqueous solutions obtained according to the present invention, however, adjust the shortage or excess of hydrogen ions resulting from oxidation-reduction reactions of chlorine oxides while buffering the pH within a narrow range. Consequently, stabilization of pH contributes to preserving the transitional state of chlorous acid (HClO2): H++ClO2−⇄HClO2, and this allows for maintaining the chlorous acid content by sustaining the stoichiometric balance of molecules and ions in the aqueous chlorous acid solution.
These observations argue that the process of the present invention exhibits superiority in providing an aqueous solution that has a high bactericidal activity and an extended stability of chlorous acid (HClO2).
The present invention achieves a long-term stabilization of chlorous acid, which has a high bactericidal potential. It will, therefore, enable commercial distribution of aqueous chlorous acid solutions on the market that have not been successfully circulated as sales products. It will contribute to widespread social adoption of chlorous acid, which is useful as disinfectant.
So far, the present invention has been explained based on embodiments with reference figures and tables. However, the present invention is not restricted to these implementations, and can be practiced in various modes within the scope of the accompanying claims.
The aqueous chlorous acid solution obtained according to the present invention can be applied for bleaching, removal of bloodstains, and other similar uses, in addition to bactericidal purposes.
| Number | Date | Country | Kind |
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| 2006-231280 | Aug 2006 | JP | national |
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| PCT/JP2007/066691 | 8/28/2007 | WO | 00 | 8/30/2010 |
| Publishing Document | Publishing Date | Country | Kind |
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| WO2008/026607 | 3/6/2008 | WO | A |
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