JP4299012B2 - Chlorine dioxide water production apparatus, production method, and sterilization apparatus - Google Patents

Description

【００６４】
上記表１によれば、第一実施例から第三実施例は、比較例との対比において、「反応圧力」が異なる場合について示されている。すなわち、「反応温度」が１０℃で「滞留時間」が１０分である場合、「反応圧力」が１．０ｋｇｆ／ｃｍ²の場合には、「反応効率」は６８％となるが（比較例）、「反応圧力」を上昇させることによって、「反応効率」は、８６％（第一実施例）、９２％（第二実施例）、９４％（第三実施例）に高めることができる。
この結果から、「反応温度」が１０℃で「滞留時間」が１０分である場合、８５％以上の「反応効率」を得るためには、２．０ｋｇｆ／ｃｍ²以上の「反応圧力」下において、上記製造方法を実施することが好ましいことが明らかとなった。また、より好ましくは、２．５ｋｇｆ／ｃｍ²以上の「反応圧力」下において、上記製造方法を実施することである。このより好ましい構成（２．５ｋｇｆ／ｃｍ²以上）によれば、９０％以上の「反応効率」を実現可能となる。
【００６６】
また、上記表１によれば、第四実施例は、「反応圧力」を高めた場合が示されている。この第四実施例によれば、「反応温度」が１５℃で「滞留時間」が１０分である場合、「反応圧力」を上昇させることによって（２．０ｋｇｆ／ｃｍ^２）、「反応効率」は、９１％に高めることができる。
この結果から、「反応温度」が１５℃で「滞留時間」が１０分である場合、９０％以上の「反応効率」を得るためには、２．０ｋｇｆ／ｃｍ^２以上の「反応圧力」下において、上記製造方法を実施することが好ましいことが明らかとなった。
【００６７】
また、上記表１によれば、第五実施例は、第四実施例との対比において、さらに「反応圧力」を高めた場合が示されている。この第五実施例によれば、「反応温度」が１５℃で「滞留時間」が１０分である場合、「反応圧力」をさらに上昇させることによって（３．０ｋｇｆ／ｃｍ^２）、「反応効率」は、９９％（第四実施例は９１％である。）に高めることができる。
この結果から、「反応温度」が１５℃で「滞留時間」が１０分である場合、９９％以上の「反応効率」を得るためには、３．０ｋｇｆ／ｃｍ^２以上の「反応圧力」下において、上記製造方法を実施することが好ましいことが明らかとなった。
【００６８】
また、上記表１によれば、第六実施例は、第三実施例との対比において、「滞留時間」を長くした場合が示されている。この第六実施例によれば、「反応圧力」が３．０ｋｇｆ／ｃｍ^２で「反応温度」が１０℃である場合、「滞留時間」を長く設定することによって、「反応効率」は、９７％（第三実施例は９４％である。）に高めることができる。
この結果から、「反応圧力」が３．０ｋｇｆ／ｃｍ^２で「反応温度」が１０℃である場合、９５％程度以上の「反応効率」を得るためには、２０分以上の「滞留時間」下において、上記製造方法を実施することが好ましいことが明らかとなった。
【００６９】
また、上記表１によれば、第七実施例は、比較例との対比においては、「反応圧力」、「反応温度」、および「滞留時間」の全ての設定条件を高め、第六実施例との対比においては、「反応温度」が高められた状態が示されている。この第七実施例によれば、「反応圧力」を３．０ｋｇｆ／ｃｍ^２、「反応温度」を１５℃、および「滞留時間」を２０分に設定することによって、「反応効率」は、１００％に高めることができる。
【００７０】
以上のことから、本実施例によれば、「滞留時間」を１０分に設定して９０％以上の「反応効率」を得ようとする場合、「反応温度」が１０℃以上のときには、「反応圧力」を２．５ｋｇｆ／ｃｍ²以上に設定することが好ましい。また、「反応温度」が１５℃以上のときには、「反応圧力」を２．０ｋｇｆ／ｃｍ²以上に設定することが好ましい。
【００７１】
【発明の効果】
以上説明したように本発明によれば、２液法を用いることによって設備の煩雑さおよびランニングコスト等の上昇を抑えつつ、反応速度を向上させることが可能であって、亜塩素酸イオンの残存量が少ない、二酸化塩素水の製造装置及び製造方法を得ることができる。また、本発明によれば、かかる製造方法にて得られた二酸化塩素水を用いて、効果的に殺菌処理を行う殺菌装置を得ることができる。
【図面の簡単な説明】
【図１】本発明の実施形態にかかる二酸化塩素水の製造方法を実現するために構成された製造装置の概略図である。
【図２】図１に示された製造装置を成す加熱反応器の概略拡大図である。
【符号の説明】
１１…第一ポンプ
１２…第二ポンプ
２１…薬液混合器
３０…加熱装置
３１…加熱反応器
３１Ａ…一端部
３１Ｂ…本体部
３１Ｃ…他端部
３２…加熱槽
４１…希釈水配管部
５１〜５４…第一〜第四配管部
５５…加熱槽蓋
６１〜６３…第一〜第三リリーフ弁
６４…低圧リリーフ弁[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to chlorine dioxide water for producing chlorine dioxide water by reacting an inorganic acid and an aqueous alkali chlorite solution.Manufacturing equipment andProduction method,AndThe present invention relates to a sterilizer that performs sterilization using chlorine dioxide water obtained by such a method.
[0002]
[Prior art]
Conventionally, it is used as a cleaning sterilizer for shells of raw vegetables, citrus fruits, eggs, etc., and as a sterilizing agent effective for sterilizing pool water, sodium hypochlorite or calcium hypochlorite ( Bleached powder) is well known. In recent years, sodium hypochlorite has become the mainstream as a disinfectant for clean water and pool water.
[0003]
Specifically, for example, when sterilizing pool water, highly bleached powder, fine powder such as trichloroisocyanuric acid, etc. are tableted to a diameter of about 20 mm and a thickness of about 10 to 20 mm, and this tablet is put into the pool. Sterilization treatment is performed. For such sterilization of pool water, the legal standard is “the free residual chlorine concentration is 0.4 mg / l or more. It is desirable that the concentration is 1.0 mg / l”. Therefore, the input amount of the tablet is adjusted so that the free residual chlorine concentration falls within this range.
In addition, sodium hypochlorite is frequently used in food factories and the like as a sterilizing and cleaning agent for vegetables and tableware.
[0004]
As described above, sodium hypochlorite is generally used for sterilization of drinking water, vegetables, etc., but if attention is not paid to the amount or location of use, trihalomethane may be produced. There is.
[0005]
For example, if this sodium hypochlorite is used as a disinfectant for clean water in a poor water quality such as a river intake, trihalomethane may be generated.
Even when sterilizing pool water, conventional chlorine disinfection requires a large amount of energy for oxidative decomposition of organic matter, and as a result of the reaction, trihalomethane may be generated.
[0006]
Therefore, recently, chlorine dioxide is being used as a chemical (disinfectant) to replace sodium hypochlorite.
For example, in Germany, Italy, France, Scandinavia (Sweden, Denmark, etc.), the United States, Canada, and South Korea, chlorine dioxide sterilization is used for sterilization of clean water, and this tendency is also worldwide (trends for chlorine dioxide sterilization). ) Is getting darker.
[0007]
In Japan as well, the legal standard for chlorine dioxide sterilization is that the residual amount of chlorine dioxide is 2.0 mg / l or less. In addition, chlorite ions are 0.2 mg / l or less. On February 26, 2012, the ministerial decree (Ministry of Health and Welfare) stipulates technical standards for water supply facilities. This is still a clean water disinfectant, but it is approved for the purpose of precipitation removal of Mn (manganese) and Fe (iron).
Also, in Japan, the use of sterilization of pools is permitted in general and public institution pools according to the “Regarding Sanitation Standards for Swimming Pools, Ministry of Health and Welfare” (applicable on July 1, 1992). Is defined as “the chlorine dioxide concentration is 0.1 mg / l or more and 0.4 mg / l or less, and the chlorous acid concentration in water is 1.2 mg / l or less”. .
[0008]
[Problems to be solved by the invention]
At present, a chemical called stabilized chlorine dioxide is well known as a disinfectant containing chlorine dioxide as an active ingredient. This drug is also sodium chlorite (NaClO)₂In the case of use, for example, sodium chlorite has no sterilizing power unless chlorine dioxide is generated according to the following reaction formula. The following four formulas have been proposed for the reaction for generating chlorine dioxide.
[0009]
Method using acid
5NaClO₂ + 4HCl → 4ClO₂ + 5NaCl + 2H₂O (1)
10NaClO₂ + 5H₂SO_Four → 8ClO₂ + 5Na₂SO_Four + 4H₂O (2)
Method using chlorine
2NaClO₂ + Cl₂ → 2ClO₂ + 2NaCl (3)
Method using sodium hypochlorite and hydrochloric acid
2NaClO₂ + NaClO + 2HCl → 2ClO₂ + 3NaCl + H₂O (4)
[0010]
In the above reaction, theoretically chlorine gas (Cl₂) And sodium chlorite react quickly, the above equation (3) is the reaction with chlorine gas, and the above equation (4) is the reaction between hydrochloric acid (HC1) and sodium hypochlorite to release chlorine gas. The chlorine gas is reacted with sodium chlorite to extract chlorine dioxide.
In Japan, the method of using chlorine gas of the above formula (3) is a rapid switch from using chlorine gas to sodium hypochlorite in water purification plants or pools from the viewpoint of chlorine gas leakage and safety. However, it is not possible at present. In the case of the above formula (4), although the reaction efficiency is good, since three chemical solutions are used, the running cost is high, the equipment is complicated, the operation management is difficult, and the equipment cost is high.
[0011]
On the other hand, the methods of the above formulas (1) and (2) are slow in reaction time but use only two chemical solutions, so that the running cost is low, the equipment is simple, and the operation management is easy. However, the reaction rate between these chemicals is very important for the generation of chlorine dioxide. If the reaction rate is low, unreacted chlorite ions remain and it is difficult to produce a large amount of chlorine dioxide water at high speed. The problem arises.
[0012]
When using sodium chlorite aqueous solution or stabilized chlorine dioxide, it is stable in alkalinity, but in this state, chlorite ion (ClO₂ ^-) Is weak in sterilization power. Therefore, activation is carried out according to any one of the reaction formulas (1) to (4) above, and a chlorine dioxide gas obtained by the chemical reaction and a reaction solution containing the chlorine dioxide gas are generated, and this is continuously added to water. Usually, it is diluted to a predetermined concentration and used.
[0013]
At this time, for the sterilization of clean water, the remaining amount of chlorite ions is 0.2 mg / l or less according to the WHO regulations, so it must be a complete chlorine dioxide aqueous solution. For sterilization washing of vegetables, etc.₂ ^-Is not left. Therefore, when sterilizing with chlorine dioxide, a production method in which chlorite ions do not remain is desired.
[0014]
  Therefore, the present invention has been made to solve the above-described problems of the prior art, and by using the two-component method, the reaction rate can be improved while suppressing the complexity of equipment and running costs. Is possible, and there is little residual amount of chlorite ion, chlorine dioxide waterManufacturing equipment andIt is an object to provide a manufacturing method.
  Moreover, this invention makes it a subject to provide the sterilizer which performs sterilization using the chlorine dioxide water obtained by this manufacturing method.
[0015]
[Means for Solving the Problems]
  That is, the chlorine dioxide water manufacturing apparatus according to the present invention transports an inorganic acid and has a first piping part having a first relief valve in the middle part, and transports an aqueous alkali chlorite solution and a second relief in the middle part. The second piping part having a valve, the first piping part and the second piping part are connected, and the inorganic acid transported from the first piping part and the alkali chlorite aqueous solution transported from the second piping part A chemical liquid mixer to be mixed, a third piping part for transporting the mixed solution mixed by the chemical liquid mixer, and a heating reactor composed of a spiral tube for the mixed solution transported from the third piping part; The heating reactor is heated by a heating tank that is immersed and heated, and is obtained by heating the heating deviceChlorine dioxide gas and aqueous reaction mixtureIn addition to being transported, it is transported by the fourth piping section having the third relief valve in the middle and the fourth piping section.Chlorine dioxide gas and reaction mixture aqueous solutionA low pressure relief valve having a set pressure lower than that of the third relief valve is provided downstream of the third relief valve of the fourth piping portion. The mixed solution is mixed between the first relief valve, the second relief valve, and the third relief valve.147 kPa to 980 kPaBy pressurizing with the pressure of and heating with a heating device,Chlorine dioxide gas and reaction mixture aqueous solutionProduces thisChlorine dioxide gas and reaction mixture aqueous solutionInto the dilution water piping downstream of the low pressure relief valve to dilute to a predetermined concentration of chlorine dioxide aqueous solution, and the low pressure relief valve causes the fluid in the dilution water piping to flow back upstream from the low pressure relief valve. It is characterized by being comprised so that it may prevent.
  The present invention also provides a method for producing chlorine dioxide water using the chlorine dioxide water production apparatus, wherein the inorganic acid and the alkali chlorite aqueous solution are supplied via the chemical liquid mixer. Mixing step of mixing,After the mixing step, a heating step of heating the inorganic acid and the alkali chlorite aqueous solution through the heating device;The inorganic acid and the aqueous alkali chlorite solution are passed through the first relief valve, the second relief valve, and the third relief valve.147 kPa to 980 kPaA pressurizing step for applying pressure, and the mixing step and the pressurizing step via the dilution water piping sectionAnd heating processObtained throughChlorine dioxide gas and reaction mixture aqueous solutionAnd a dilution step for diluting the liquid.
[0016]
According to such a configuration, since it is a two-component method, it is possible to suppress an increase in cost. By having the pressurizing step, the reaction efficiency is increased, and in a shorter time, Chlorine dioxide water with a small remaining amount of acid ions can be obtained.
[0017]
Moreover, in the manufacturing method of the chlorine dioxide water concerning this invention, the pressure at the time of performing the said pressurization process is 147 kPa (1.5 kgf / cm²) To 980 kPa (10 kgf / cm²) Is preferable.
[0018]
Moreover, in the manufacturing method of the chlorine dioxide water concerning this invention, the structure whose residence time required for the said pressurization process is 10 minutes or more is preferable.
[0019]
  According to the method for producing chlorine dioxide water according to the present invention, since it is a two-component method, it is possible to suppress an increase in cost. Chlorine dioxide water can be produced satisfactorily with a configuration having a pressure step and the like.
  On the other hand, when the room temperature of the installation place is lower than 10 ° C., the reaction efficiency is slightly lowered. Therefore, as described above, it is preferable to include a heating step of heating the inorganic acid and the alkali chlorite aqueous solution. According to this preferred configuration, by having the heating step together with the pressurizing step, the reaction efficiency can be further increased, and chlorine dioxide water with a small amount of remaining chlorite ions can be obtained in a shorter time.
[0020]
  AlsoThisAccording to the preferable configuration, since the heating step is performed after the mixing step, the above-described effects can be obtained by providing only one heating device or the like.
[0022]
Moreover, in the manufacturing method of the chlorine dioxide water concerning this invention, the structure at the time of performing the said heating process is 20 to 40 degreeC is preferable.
[0023]
Furthermore, the sterilization apparatus according to the present invention is characterized in that chlorine dioxide water obtained by any one of the above-described chlorine dioxide water production methods is configured to be directly injected into a circulation line to be sterilized. Yes.
[0024]
In the sterilization apparatus according to the present invention, it is preferable that the object to be sterilized is a hot spring, a bath, or a pool.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have intensively studied to solve the problem and have arrived at the present invention. According to the present invention, a two-liquid method (that is, sodium chlorite and an inorganic acid (hydrochloric acid) having a slow reaction rate is used. Etc.) can be realized) by producing a chlorine dioxide water production method in which chlorite ions do not remain.
Specifically, by appropriately adjusting the reaction pressure when the chemical solution is reacted (by performing a pressurizing step), the reaction efficiency is improved and the amount of acid used for activation is reduced. Found that is possible. In addition, it has been found that by appropriately adjusting the reaction temperature, the reaction time, etc. together with the reaction pressure, it is possible to reduce the amount of acid used for activation when producing chlorine dioxide water. .
[0026]
For example, the pressure during the pressurizing step is 147 kPa (1.5 kgf / cm²) To 980 kPa (10 kgf / cm²), It is found that the reaction efficiency can be improved. More preferably, the pressure during the pressurizing step is 245 kPa (2.5 kgf / cm²) To 785 kPa (8 kgf / cm²) It was found that it was set to a degree.
Further, the pressure during the pressurizing step is 147 kPa (1.5 kgf / cm²It was confirmed that when it was set to a value smaller than), it did not contribute much to the reaction efficiency. Furthermore, the pressure during the pressurizing step is 980 kPa (10 kgf / cm²It was also confirmed that a particularly large improvement in reaction efficiency could not be expected even when the value was set to a value larger than).
[0027]
Furthermore, in winter conditions where the temperature is low (for example, about 5 ° C.), the reaction efficiency is not significantly improved by increasing the pressure, but if the reaction temperature or the like when reacting the chemical is appropriately adjusted (heating) If a process etc. are implemented), reaction efficiency can be improved. For example, if the reaction temperature is heated to about 12 ° C., the generation efficiency of chlorine dioxide can be improved to about 97%. At this time, each apparatus is configured such that the reaction time (residence time until the dilution step described later) for producing chlorine dioxide water is, for example, 10 minutes or more (for example, a heating reactor). The tube length has been adjusted.)
[0028]
The sodium chlorite used in the present invention is 7% to 25% NaClO of a commercial product.₂9% to 35% HCl can be used as hydrochloric acid, but it is convenient to use a commercially available 9% to 15% HCl as hydrochloric acid from the viewpoint of handling. preferable.
[0029]
Hereinafter, a specific manufacturing apparatus will be described in detail based on the drawings.
[0030]
FIG. 1 is a schematic view of a production apparatus configured to realize a method for producing chlorine dioxide water according to an embodiment of the present invention.
As shown in FIG. 1, the manufacturing apparatus according to the present embodiment includes a first pump 11 that conveys hydrochloric acid (HCl) (corresponding to the “inorganic acid” of the present invention), and sodium chlorite (NaClO).₂) (Corresponding to “alkaline chlorite aqueous solution” of the present invention), and a chemical liquid mixer 21 for mixing hydrochloric acid and sodium chlorite conveyed by the respective pumps 11 and 12; The heating device 30 that heats the mixed solution on the downstream side of the chemical liquid mixer 21 and the dilution water pipe portion 41 that performs the dilution processing on the downstream side of the heating device 30 are configured. Moreover, the heating apparatus 30 is comprised using the heating reactor 31 comprised so that insertion of a mixed solution and the heating tank 32 which can immerse this heating reactor 31 were comprised.
[0031]
More specifically, the first pump 11 and the chemical liquid mixer 21 are connected via the first piping part 51, and the second pump 12 and the chemical liquid mixer 21 are connected via the second piping part 52. Each aqueous solution is conveyed from each pump 11, 12 to each chemical solution mixer 21 via each pipe 51, 52. The first piping part 51 is provided with a first relief valve 61, and the second piping part 52 is provided with a second relief valve 62. Here, as the first relief valve 61 and the second relief valve 62, for example, “3 kgf / cm”²A “relief valve” is used.
[0032]
The mixed solution mixed in the chemical liquid mixer 21 is conveyed to the heating reactor 31 through the third piping unit 53, and the mixed solution inserted through the heating reactor 31 is diluted through the fourth piping unit 54. It is conveyed to the water piping part 41. The fourth piping portion 54 is provided with a third relief valve 63 and a low pressure relief valve 64. Here, for example, as the third relief valve 63, “3 kgf / cm²“Relief valve” is used, and the low pressure relief valve 64 is “1.5 kgf / cm”.²A “relief valve” is used.
[0033]
The 1st and 2nd pumps 11 and 12 are comprised using the wetted part etc. with high corrosion resistance, respectively. For example, a diaphragm or the like that is a wetted part is formed using a fluororesin having high corrosion resistance, and reciprocating pumps (quantitative pumps) that reciprocate the diaphragm to transport each aqueous solution are first and second pumps 11, 12 is used.
[0034]
Further, the chemical liquid mixer 21, the heating reactor 31, and each of the pipe portions 51 to 54 are also configured using a material having high corrosion resistance (for example, a fluororesin) at least in the inside thereof.
[0035]
FIG. 2 is a schematic enlarged view of the heating reactor 31. The heating reactor 31 according to this embodiment uses a fluororesin tube body, and as shown in FIG. 2, the main body 31B is formed in a spiral shape.
[0036]
The liquid mixture from the chemical liquid mixer 21 is sent to one end portion 31A of the heating reactor 31 via the third piping portion 53, and is sent to the fourth piping portion 53 via the main body portion 31B and the other end portion 31C. . That is, the mixed liquid sent to the heating reactor 31 is positively exchanged heat with the high-temperature water in the heating tank 32 in the spiral main body 31B.
[0037]
Next, a method for producing chlorine dioxide water according to the present embodiment, which is performed by the apparatus configured as shown in FIGS. 1 and 2, will be specifically described.
[0038]
The chlorite used in this embodiment is an alkali metal salt chlorite such as sodium chlorite, calcium chlorite, magnesium chlorite, potassium chlorite, etc. Examples include alkali metal chlorites, with sodium chlorite being particularly preferred. The concentration of the chlorous acid aqueous solution is usually 7 to 25% by weight.
Examples of the acid solution include various inorganic acids such as hydrochloric acid and sulfuric acid of 5 to 15%, and various organic acids such as acetic acid, citric acid, and malic acid. The inventors have found that they are not suitable for the chlorine generation reaction.
Specifically, since the organic acid is an organic substance, the decomposition reaction further proceeds. For example, in the reaction of citric acid and sodium chlorite,
15NaClO₂ + 4HO₂CC (OH) (CH₂CO₂H)₂→ 12ClO₂ + 4C₆H_FiveNa_ThreeO₇ + 3NaCl + 6H₂O
However, if the chlorine dioxide concentration is high, C₆H_FiveNa_ThreeO₇Is further decomposed and consumed, so that chlorine dioxide is consumed, and the concentration of chlorine dioxide obtained from the reaction amount decreases (less than about 2/3 compared with the case of using an inorganic acid).
Therefore, in this embodiment, as described above, an inorganic acid (for example, hydrochloric acid) is used as the acid solution used for the chlorine dioxide generation reaction.
[0039]
In the present embodiment, first, using the first pump 11 and the second pump 12, an inorganic acid storage tank (not shown) and an alkaline chlorite aqueous solution storage tank (not shown) connected to the pumps 11 and 12, respectively. Each aqueous solution in the illustration is omitted and conveyed to the chemical liquid mixer 21. At this time, since the above-described relief valves 61 and 62 are provided in the pipe portions 51 and 52 that connect the pumps 11 and 12 and the chemical liquid mixer 21, respectively, A pressure equal to or higher than the set pressure of the relief valves 61 and 62 is applied (corresponding to the “pressurizing step” of the present invention).
[0040]
Next, each aqueous solution fed and supplied through the pumps 11 and 12 and the pipe parts 51 and 52 and the relief valves 61 and 62 connected to the pumps 11 and 12 is mixed in the chemical liquid mixer 21 and then the third pipe. It is sent to the heating reactor 31 via the part 53. In the heating reactor 31, heat treatment (corresponding to the “heating step” of the present invention) is performed so that the mixed solution has an appropriate temperature.
In addition, conveyance from this chemical | medical solution mixer 21 to the heating reactor 31 is performed with the driving force of the 1st and 2nd pumps 11 and 12 so that the preset pressure of each relief valve 61 and 62 may be exceeded.
[0041]
Next, the liquid-gas mixture containing chlorine dioxide generated by the heating reaction of both (hydrochloric acid and sodium chlorite) in the heating reactor 31 is passed through the fourth pipe portion 54 as a diluent. It is injected into the diluent pipe part 41. At this time, since the third relief valve 63 is also provided in the fourth piping portion 54, a pressure exceeding the set pressure of the third relief valve 63 is applied to the liquid-gas mixture containing chlorine dioxide. Become. In addition, since the low pressure relief valve 64 is provided in the fourth piping portion 54 immediately before the dilution water piping portion 41 on the downstream side of the third relief valve 63, the fourth piping portion extends from the dilution water piping portion 41. The backflow of the fluid with respect to 54 can be prevented appropriately.
[0042]
In the present embodiment, the chlorine dioxide gas and the reaction mixture thereof can be injected and dissolved at a constant concentration in the aqueous medium by passing through the above steps. It becomes possible to produce an aqueous chlorine dioxide solution that does not contain it.
[0043]
As described above, in the present embodiment, each aqueous solution is reacted in a state in which a pressure exceeding the set pressure of each relief valve 61, 62 is applied, that is, in the pressurization region, and thus generated by the reaction. Chlorine gas dissolves in the reaction solution by gas partial pressure. Therefore, according to this embodiment, a high concentration chlorine dioxide aqueous solution can be obtained.
[0044]
That is, according to the present embodiment, in the process of reacting hydrochloric acid and sodium chlorite in the chemical liquid mixer 21, as shown in FIG. 1, a pressure (for example, 3 kgf / cm²Unless the above pressure is reached, each aqueous solution cannot be passed through the chemical liquid mixer 21. Because of such a configuration, each aqueous solution is injected under pressure by the corresponding pumps 11 and 12, and chlorine dioxide gas is dissolved in the reaction solution due to the partial pressure of the gas due to the pressure at this time. When it melts, it deviates from the explosion limit of 15% for chlorine dioxide, preventing explosion.
[0045]
In the present embodiment, the relief valves 61 to 63 are “3 kgf / cm”.²Although the case where the “relief valve” is used has been described, the present invention is not limited to this configuration, and if necessary, 1.5 kgf / cm.²-10kgf / cm²A degree relief valve may be used.
[0046]
Further, the heating reactor 31 according to the present embodiment is configured in a spiral shape as shown in FIG. 2, and in this embodiment, the spiral heating reactor 31 is provided so as to be immersed in the heating tank 32. Therefore, the liquid mixture in the heating reactor 31 is efficiently heated. That is, when the heating reactor 31 has a spiral shape, the residence time of the mixed liquid in the heating tank 32 becomes long, and heat exchange is promoted.
[0047]
Here, the length of the tube constituting the heating reactor 31 (length in a linear state) is preferably set to ensure a residence time of 10 minutes or longer, for example, about 1 to 50 m, Desirably, the distance is 5 m to 40 m. The inner diameter of the tube is preferably about 3 mm to 10 mmφ. In the present embodiment, the reaction efficiency is poor when a residence time of 10 minutes or more cannot be secured according to the length or inner diameter of the heating reactor 31. In addition, when the length of the heating reactor 31 is longer than 50 m, for example, the residence time can be sufficiently secured, but the amount of the reaction storage liquid in the pipe increases, and the concentration after dilution from the stop to the operation It takes a long time to stabilize. On the other hand, if the length is too long, the heating reactor 31 and the heating tank 32 into which the heating reactor 31 is immersed are increased in size, resulting in an increase in cost.
[0048]
Further, according to the present embodiment, the chlorine dioxide aqueous solution can be diluted to a target concentration by injecting the chlorine dioxide aqueous solution into the dilution water pipe portion 41 at a predetermined concentration. Also, the concentration of the chlorine dioxide aqueous solution can be adjusted by controlling the injection amount of each aqueous solution.
[0049]
In addition, the chlorine dioxide generation reaction is highly corrosive at high concentrations and may cause a puff (explosion) phenomenon due to photoreaction caused by light from ultraviolet rays or fluorescent lamps, so sodium chlorite The heating reactor 31 according to the present embodiment for reacting water and hydrochloric acid is formed using a material having high corrosion resistance, and is configured to shield light. Specifically, the heating reactor 31 is configured using a fluororesin tube, a titanium tube, or the like, and the heating tank 32 is heated so as to shield light and prevent evaporation of a heat medium (such as high-temperature water). A tank lid 55 is provided. For the same reason as described above, the fourth piping portion 54 is configured by using a fluororesin tube covered with a black shrinkable tube so as to have a light shielding property. Furthermore, if necessary, the third piping part 53 is also preferably configured using a fluororesin tube covered with a black shrinkable tube so as to have a light shielding property.
[0050]
Furthermore, in this embodiment, the structure which inject | pours the chlorine dioxide water obtained with the manufacturing method mentioned above directly in the circulation line of to-be-sterilized object is preferable. That is, when the object to be sterilized is a hot spring, a bath, a pool, a hot water pool, or the like, according to the present embodiment, the chlorine dioxide aqueous solution obtained through the pressurizing step or the like is added to the circulation line or this circulation line. A stable aqueous solution containing chlorine dioxide can be obtained by injecting directly into a provided filter or the like. For example, in FIG. 1, the said circulation line etc. may be provided in the downstream of the dilution water piping part 41, or the said circulation line etc. may be provided in the location in which the dilution water piping part 41 was provided.
[0051]
Now, sodium hypochlorite, which has been used for sterilization, has a very weak sterilizing power on the alkaline side, and it is damaged by Legionella in hot springs and hot water pools even though chemicals are injected. There is a risk. This is because in hot springs and hot water pools, the water temperature is maintained at about 35 ° C. to 42 ° C., and there is an environment in which biofilms and slimes are easily generated. In particular, Japanese general hot springs are often alkaline, and in such cases, conventional sterilization using sodium hypochlorite may not be effective. Therefore, a biofilm or slime becomes a place of residence for Legionella bacteria, and damage of this Legionella bacteria may occur.
[0052]
On the other hand, chlorine dioxide is characterized in that its bactericidal power does not change on the acidic side or the alkaline side, and the range in which the bactericidal power can be exhibited is about pH = 2.0-10. When pH exceeds 10, sodium chlorate (NaClO)_Three), So be careful.
Therefore, if the chlorine dioxide water obtained by the production method according to this embodiment is injected into a circulation line such as a hot spring, the biofilm that is the home of Legionella bacteria is destroyed, and Legionella bacteria and the like are effectively sterilized. Can be removed. In particular, since a biofilm or the like is easily generated in a filter provided in a circulation line such as a hot spring or a bath, in the present embodiment, it is preferable that chlorine dioxide water be injected before the filter.
[0053]
As described above, in the present embodiment, an inorganic acid (hydrochloric acid) and an aqueous alkali chlorite solution (sodium chlorite) are mixed under pressure, and the mixed solution is heated and reacted by the heating device 30. . That is, by pressurizing and heating each chemical solution, the reaction rate is increased and the reaction efficiency is increased. Thus, if the reaction efficiency is increased, it becomes possible to obtain chlorine dioxide gas and a reaction mixture aqueous solution that do not contain chlorite ions.
[0054]
In the present embodiment, a dilution water pipe 41 is provided on the downstream side of the heating device 30 in order to dilute the chlorine dioxide gas and the reaction mixture aqueous solution obtained after such a reaction with a dilute aqueous solution according to the purpose. ing. That is, by providing the dilution water pipe section 41 that can be set to an arbitrary concentration, the chlorine dioxide aqueous solution can be stably supplied at a desired concentration.
[0055]
That is, according to this embodiment, the use of the two-liquid method can suppress the complexity of the equipment and the running cost. In addition, by performing the heating reaction using the heating device 30 while performing the pressurizing step, it is possible to eliminate the slow reaction rate, which was a problem of the two-component method, and to promote the two-component reaction. Therefore, the manufacturing method of chlorine dioxide water with little residual amount of chlorite ions can be obtained.
[0056]
The present invention is not limited to the above-described embodiment, and various modifications other than those described above can be made without departing from the spirit of the present invention.
[0057]
For example, in the above-described embodiment, the case where the pressure value when pressurizing using the relief valve is set has been described. However, the present invention is not limited to this configuration. You may comprise so that the pressure value at the time of pressurization may be set using a valve etc.
[0058]
Moreover, in the said embodiment, although the case where a heating process was performed after a mixing process was demonstrated, this invention is not limited to this structure. Therefore, for example, after mixing at least one of the inorganic acid and the alkali chlorite aqueous solution, the mixing step may be performed.
[0059]
Moreover, in the said embodiment, although the case where the chemical | medical solution mixer 21 and the heating reactor 31 were provided was demonstrated, this invention is not limited to this structure, The mixing process of each aqueous solution is carried out in one container. And heat treatment may be performed. For example, you may comprise so that each aqueous solution may be directly supplied to the heating apparatus 30, without providing the chemical | medical solution mixer 21 shown in FIG. At this time, as shown in FIG. 1, if each relief valve is provided, in the heating reactor 31, the pressurizing process is also performed at the same time.
[0060]
【Example】
Next, examples of the present invention will be shown. However, the present invention is not limited by the following examples as a matter of course, and it is needless to say that the present invention can be implemented with appropriate modifications within a range that can meet the gist of the preceding and following descriptions. These are all included in the technical scope of the present invention.
[0061]
As the conditions of the examples, “9% hydrochloric acid” is used as the inorganic salt and “8% sodium chlorite” is used as the aqueous alkali chlorite solution, and a flow rate of 20.0 ml / min is flowed respectively. In each example, the “reaction pressure”, “reaction temperature”, and “residence time” (time during which the pressurization step is performed, for example, the time until the dilution step is performed) are changed, and each reaction efficiency ( The reaction efficiency as seen from the chlorite ion concentration).
As a comparative example, the “reaction pressure” is 1.0 kgf / cm using a relief valve or the like.²The “reaction temperature” was 10 ° C., and the “residence time” was 10 minutes. In this case, the “reaction efficiency” was 68%.
[0062]
  First, as a first embodiment, a “reaction pressure” is set to 2.0 kgf / cm using a relief valve or the like.²When the “reaction temperature” was 10 ° C. and the “residence time” was 10 minutes, the “reaction efficiency” was 86%.
  Next, as a second example, the “reaction pressure” is 2.5 kgf / cm.²When the “reaction temperature” was 10 ° C. and the “residence time” was 10 minutes, the “reaction efficiency” was 92%.
  Next, as a third example, the “reaction pressure” is set to 3.0 kgf / cm 3.²When the “reaction temperature” was 10 ° C. and the “residence time” was 10 minutes, the “reaction efficiency” was 94%.
  NextFourAs an example, the “reaction pressure” is 2.0 kgf / cm.²When the “reaction temperature” was 15 ° C. and the “residence time” was 10 minutes, the “reaction efficiency” was 91%.
  NextFiveAs an example, the “reaction pressure” is set to 3.0 kgf / cm.²When the “reaction temperature” was 15 ° C. and the “residence time” was 10 minutes, the “reaction efficiency” was 99%.
  NextSixAs an example, the “reaction pressure” is set to 3.0 kgf / cm.²When the “reaction temperature” was 10 ° C. and the “residence time” was 20 minutes, the “reaction efficiency” was 97%.
  NextSevenAs an example, the “reaction pressure” is set to 3.0 kgf / cm.²When the “reaction temperature” was 15 ° C. and the “residence time” was 20 minutes, the “reaction efficiency” was 100%.
  The above examples and comparative examples are summarized as shown in Table 1 below. From Table 1, the following becomes clear.
[0063]
[Table 1]

[0064]
According to Table 1 above, the first to third examples show cases where the “reaction pressure” is different in comparison with the comparative example. That is, when the “reaction temperature” is 10 ° C. and the “residence time” is 10 minutes, the “reaction pressure” is 1.0 kgf / cm.²In this case, the “reaction efficiency” is 68% (comparative example), but by increasing the “reaction pressure”, the “reaction efficiency” is 86% (first example) and 92% (second example). Example) can be increased to 94% (third example).
From this result, when the “reaction temperature” is 10 ° C. and the “residence time” is 10 minutes, in order to obtain “reaction efficiency” of 85% or more, 2.0 kgf / cm²It became clear that it is preferable to carry out the above production method under the above “reaction pressure”. More preferably, it is 2.5 kgf / cm.²The above production method is carried out under the above “reaction pressure”. This more preferable configuration (2.5 kgf / cm²According to the above, “reaction efficiency” of 90% or more can be realized.
[0066]
  Also, according to Table 1 above,FourIn the examples, the case where the “reaction pressure” is increased is shown. This firstFourAccording to the examples, when the “reaction temperature” is 15 ° C. and the “residence time” is 10 minutes, by increasing the “reaction pressure” (2.0 kgf / cm²), “Reaction efficiency” is 91ToCan be increased.
  From this result, when “reaction temperature” is 15 ° C. and “residence time” is 10 minutes, in order to obtain “reaction efficiency” of 90% or more, 2.0 kgf / cm²It became clear that it is preferable to carry out the above production method under the above “reaction pressure”.
[0067]
  Also, according to Table 1 above,FiveThe fourth embodimentExamples andIn contrast, the case where the “reaction pressure” is further increased is shown. This firstFiveAccording to the examples, when the “reaction temperature” is 15 ° C. and the “residence time” is 10 minutes, by further increasing the “reaction pressure” (3.0 kgf / cm²), "Reaction efficiency" is 99% (No.FourThe example is 91%. ) Can be increased.
  From this result, when “reaction temperature” is 15 ° C. and “residence time” is 10 minutes, in order to obtain “reaction efficiency” of 99% or more, 3.0 kgf / cm²It became clear that it is preferable to carry out the above production method under the above “reaction pressure”.
[0068]
  Also, according to Table 1 above,SixThe example shows a case where the “residence time” is increased in comparison with the third example. This firstSixAccording to the examples, the “reaction pressure” is 3.0 kgf / cm.²When the “reaction temperature” is 10 ° C., the “reaction efficiency” can be increased to 97% (the third example is 94%) by setting the “residence time” longer.
  From this result, the “reaction pressure” is 3.0 kgf / cm.²When the “reaction temperature” is 10 ° C., in order to obtain “reaction efficiency” of about 95% or more, it is clear that the above production method is preferably carried out under a “residence time” of 20 minutes or more. It became.
[0069]
  Also, according to Table 1 above,SevenIn comparison with the comparative example, the examples increased all the setting conditions of “reaction pressure”, “reaction temperature”, and “residence time”.SixIn contrast to the examples, a state in which the “reaction temperature” is increased is shown. This firstSevenAccording to the examples, the “reaction pressure” is 3.0 kgf / cm.²By setting the “reaction temperature” to 15 ° C. and the “residence time” to 20 minutes, the “reaction efficiency” can be increased to 100%.
[0070]
From the above, according to this example, when setting the “residence time” to 10 minutes and obtaining “reaction efficiency” of 90% or higher, when the “reaction temperature” is 10 ° C. or higher, Reaction pressure "is 2.5 kgf / cm²It is preferable to set the above. When the “reaction temperature” is 15 ° C. or higher, the “reaction pressure” is 2.0 kgf / cm.²It is preferable to set the above.
[0071]
【The invention's effect】
  As described above, according to the present invention, by using the two-component method, it is possible to improve the reaction rate while suppressing the complexity of the equipment and the increase in running cost, and the residual chlorite ion. A small amount of chlorine dioxide waterManufacturing equipment andA manufacturing method can be obtained. Moreover, according to this invention, the sterilization apparatus which performs an effective sterilization process can be obtained using the chlorine dioxide water obtained by this manufacturing method.
[Brief description of the drawings]
FIG. 1 is a schematic view of a production apparatus configured to realize a method for producing chlorine dioxide water according to an embodiment of the present invention.
2 is a schematic enlarged view of a heating reactor constituting the production apparatus shown in FIG. 1. FIG.
[Explanation of symbols]
11 ... The first pump
12 ... Second pump
21 ... Chemical liquid mixer
30 ... Heating device
31 ... Heating reactor
31A ... one end
31B ... Main unit
31C ... the other end
32 ... Heating tank
41 ... dilution water piping
51-54 ... 1st-4th piping part
55 ... Heating tank lid
61-63 ... 1st-3rd relief valve
64 ... Low pressure relief valve

Claims (6)

A first piping part for conveying an inorganic acid and having a first relief valve in the middle part;
A second piping part for conveying an aqueous solution of alkali chlorite and having a second relief valve in the middle part;
A chemical solution mixer for mixing the inorganic acid conveyed from the first piping part and the alkali chlorite aqueous solution conveyed from the second piping part, together with the first piping part and the second piping part connected,
A third piping part for conveying the mixed solution mixed by the chemical liquid mixer;
A heating device that heats the mixed solution conveyed from the third piping section by a heating reactor configured by a spiral tube and a heating tank in which the heating reactor is immersed and heated;
A fourth piping part that conveys chlorine dioxide gas obtained by heating of the heating device and the reaction mixture aqueous solution, and has a third relief valve in the middle part,
A dilution water piping section for diluting the chlorine dioxide gas and the reaction mixture aqueous solution conveyed by the fourth piping section,
On the downstream side of the third relief valve of the fourth piping part, a low pressure relief valve having a lower set pressure than the third relief valve is provided,
The mixed solution mixed by the chemical liquid mixer is pressurized at a pressure of 147 kPa to 980 kPa between the first relief valve, the second relief valve, and the third relief valve, and is heated by a heating device. The chlorine dioxide gas and the reaction mixture aqueous solution are generated, and the chlorine dioxide gas and the reaction mixture aqueous solution are diluted into a chlorine dioxide aqueous solution having a predetermined concentration by flowing into the dilution water piping section downstream of the low pressure relief valve. An apparatus for producing chlorine dioxide water, wherein the relief valve is configured to prevent the fluid in the dilution water piping section from flowing back upstream from the low pressure relief valve. A chlorine dioxide water production method for producing chlorine dioxide water using the chlorine dioxide water production apparatus according to claim 1,
A mixing step of mixing the inorganic acid and the alkali chlorite aqueous solution through the chemical liquid mixer;
After the mixing step, a heating step of heating the inorganic acid and the alkali chlorite aqueous solution through the heating device;
A pressurizing step of applying a pressure of 147 kPa to 980 kPa to the inorganic acid and the aqueous alkali chlorite solution through the first relief valve, the second relief valve, and the third relief valve;
A dilution step for diluting the chlorine dioxide gas and the reaction mixture aqueous solution obtained through the mixing step, the pressurizing step , and the heating step through the dilution water piping section;
A method for producing chlorine dioxide water. Residence time required for the pressurization step is 10 minutes or more
The method for producing chlorine dioxide water according to claim 2 . The temperature at the time of performing the heating step is 20 ° C to 40 ° C.
The method for producing chlorine dioxide water according to claim 2 or 3 . Sterilization characterized in that chlorine dioxide water obtained by the method for producing chlorine dioxide water according to any one of claims 2 to 4 is directly injected into a circulation line to be sterilized. apparatus. The sterilization apparatus according to claim 5, wherein the object to be sterilized is a hot spring, a bath, or a pool.

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