200902453 (1) 九、發明說明 【發明所屬之技術領域】 本發明是關於利用無隔膜電解槽，將鹽酸予以電解， 用水來稀釋所生成的電解液，以生成微酸性電解水之方法 及裝置，特別是關於用所生成的微酸性電解水來稀釋原料 鹽酸，作爲電解原液之方法及裝置。 【先前技術】 利用無隔膜電解槽，將鹽酸予以電解，以生成微酸性 電解水的方法，在日本專利文獻1中已有揭示。 另外，日本專利文獻2中揭示：利用無隔膜電解槽， 將食鹽溶液與鹽酸混合在一起的溶液予以電解，以生成酸 性的電解水之方法，該法方可獲得殘留氯爲1.0~200 ppm 且pH値爲3〜7的電解殺菌水。 進而，日本專利文獻3中揭示：在將一定濃度的電解 質溶液予以電解所獲得之酸性電解水中，添加入無機酸的 緩衝液，以將pH値調整成3.5〜5.5之方法。該方法之目 的是調整氫離子濃度，以使存在於酸性電解水中之次氯酸 穩定。 專利文獻1:日本專利特開平10-128336號公報 專利文獻2 :日本專利特開平5 — 2 3 7 4 7 8號公報 專利文獻3:日本專利特開平1〇 — 309582號公報 【發明內容】 -4- 200902453 (2) <發明所欲解決之課題> 將食鹽、鹽酸等含有氯離子的溶液予以電解，以生成 含有次氯酸的電解水的方法已有多種揭示。然而，已知次 氯酸在單體的狀態下存在時呈現最強的殺菌效果，不過該 存在比率係處在依賴於液體的pH値的平衡關係，在鹼性 側時會成爲幾乎沒有殺菌力的次氯酸離子，在pH値爲4 以下的酸性側時會成爲氯氣並在短時間內就逸散。因此， 爲了要使殺菌力穩定的次氯酸存在，必須將pH値維持在 4〜6.5程度。 然則，日本專利文獻1的技術，由於只將鹽酸予以電 解，被認爲會引起以下的反應。 (陽極表面）2C1— — Cl2 + 2e......化學式1 所生成的氯將會立即與水起反應，如同下述化學式， 產生次氯酸及鹽酸。200902453 (1) IX. Description of the Invention [Technical Fields of the Invention] The present invention relates to a method and apparatus for producing slightly acidic electrolyzed water by electrolyzing hydrochloric acid using a diaphragmless electrolytic cell and diluting the generated electrolytic solution with water. In particular, it relates to a method and apparatus for diluting a raw material hydrochloric acid with the produced slightly acidic electrolyzed water as an electrolytic stock solution. [Prior Art] A method of electrolyzing hydrochloric acid by a diaphragmless electrolytic cell to produce slightly acidic electrolyzed water has been disclosed in Japanese Patent Laid-Open No. Hei. Further, Japanese Patent Laid-Open No. Hei 2 discloses that a solution in which a salt solution is mixed with hydrochloric acid is electrolyzed by a non-diaphragm electrolytic cell to produce acidic electrolyzed water, which can obtain residual chlorine of 1.0 to 200 ppm. Electrolytic sterilizing water having a pH of 3 to 7. Further, Japanese Patent Laid-Open No. 3 discloses a method of adding a buffer solution of a mineral acid to an acidic electrolyzed water obtained by electrolyzing a certain concentration of an electrolytic solution to adjust the pH to 3.5 to 5.5. The purpose of this method is to adjust the hydrogen ion concentration to stabilize the hypochlorous acid present in the acidic electrolyzed water. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 10-128336 (Patent Document 2) Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. 4-200902453 (2) <Problems to be Solved by the Invention> A method of electrolyzing a solution containing chloride ions such as salt or hydrochloric acid to produce electrolyzed water containing hypochlorous acid has been disclosed. However, it is known that hypochlorous acid exhibits the strongest bactericidal effect in the presence of a monomer, but the ratio of existence is in a pH-dependent equilibrium relationship with a liquid, and on the alkaline side, it becomes almost bactericidal. The hypochlorite ion becomes chlorine gas when it has an acid side of pH 4 of 4 or less and escapes in a short time. Therefore, in order to stabilize the bactericidal power of hypochlorous acid, it is necessary to maintain the pH 4 at a level of 4 to 6.5. However, the technique of Japanese Patent Document 1 is considered to cause the following reaction because only hydrochloric acid is electrolyzed. (Anode surface) 2C1 - Cl2 + 2e... The chlorine formed in Chemical Formula 1 will immediately react with water, producing hypochlorous acid and hydrochloric acid like the following chemical formula.
Cl2 + H20 — HOC1 + HC1 ......化學式 2 因此，使用電解液、稀釋電解液之後才使用的情況， 在稀釋水中若不含具有緩衝作用的成分的話，將會變成異 常低的pH値，且會導致脫離單體的次氯酸得以穗定地存 在的區域。 曰本專利文獻2的方法，其目的被認爲是藉由在電解 200902453 (3) 原液中不僅包含鹽酸還混入食鹽，來補足日本專利文獻1 所揭示的技術中的缺點，不過作爲氯離子源的話，若沒有 比鹽酸還要更大幅地增多食鹽的量的話，則達不到pH値 的上升效果。因此，在所生成的電解水中含有相當程度量 之來自原料的Na，乾燥後會殘留固態物，所以非常缺乏 便利性。另外，必須使用2種藥劑，故無法避免裝置的複 雜化、控制上的複雜化。 另一方面，日本專利文獻3的技術，必須在電解水生 成的後續步驟中設置緩衝液的添加步驟，無法避免裝置的 複雜化、大型化，再則必須在添加步驟中，一面確認pH 値等，一面添加緩衝液，所以當然控制上也會變複雜。因 此，可預測裝置將會大型化、高價化。另外，所添加的緩 衝液爲固態物的溶液，所以，與日本專利文獻2所揭示的 技術相同，會有引起在使用電解水之後析出固態物的弊端 之危險性。 於是，本發明所要解決的課題，是在於提供：不會導 致裝置的複雜化、控制上的複雜化，且不必在電解水中添 加含有固態物的藥劑，就可生成具有次氯酸得以穩定存在 的pH値範圍之微酸性電解水之方法及裝置。 <用以解決課題之手段> 鹽酸經電解過後，用水來稀釋且生成微酸性電解水時 所引起的反應，如同上述的化學式1和化學式2。在稀釋 過後的階段，會成爲含有與次氯酸相同莫耳濃度的鹽酸。 -6- 200902453 (4) 於是，將所生成的微酸性電解水的一部分再度引導到電解 槽中並進行電解，藉由此方式，能夠減少最終的鹽酸量。 已知的鹽酸的電解方式，在進行電解之前就用稀釋水的一 部分來將較高濃度的鹽酸，一面稀釋一面進行電解的方 法，不過當然要將該稀釋所用的水，改換成採用所生成的 微酸性電解水。依據這種方式，例如藉由電解原液的導電 度來控制電解電流的情況，以微酸性電解水取代水來進行 稀釋的話，依微酸性電解水的導電度高於水的（導電度）程 度減少鹽酸的使用量，也可預期所生成的微酸性電解水的 pH値會上升。 於是，用來解決課題之本發明的第1技術方案，是一 種利用無隔膜電解槽，將含有食鹽或/和食鹽以外的無機 成分之鹽酸予以電解，用水來稀釋所生成的電解液，以生 成微酸性電解水的方法，將使用所生成的微酸性電解水的 一部分來進行稀釋過的鹽酸，作爲電解原液。 使用含有食鹽或/和食鹽以外的無機成分之鹽酸是因 含在鹽酸本身的無機成分裡面，例如鹼性金屬或鹼土類金 屬會有藉由電解而成爲鹼性成分，與鹽酸的一部分起反 應’幫助pH値上升的舉動之故。該鹽酸並不是特別地添 加無機成分來進行調整的，而是在稀釋鹽酸時的稀釋水使 用，例如：硬水、海洋深層水之類的含有無機成分的水， 藉此方式來獲得無機成分。 其次’用來解決課題之本發明的第2技術方案，是使 用所生成的微酸性電解水來稀釋鹽酸的工作、及電解稀釋 200902453 (5) 過的鹽酸的工作以及生成微酸性電解水的工作，分別連續 地進行。藉由此方式’能夠連續地生成PH値穩定的微酸 性電解水。爲了要用微酸性電解水來將鹽酸予以一面稀釋 —面電解，也可以例如：在讓電解液混合在稀釋水中的步 驟的後續步驟中，連接稀釋用電解水的取出管路，將該管 路的另一端連接到鹽酸供應流路。 如第1圖所示，鹽酸藉由泵浦來供應之構造的情況’ 可以在鹽酸供應泵浦的下游之鹽酸供應管路連接稀釋用電 解水取出管路，藉由裝備在稀釋用電解水取出管路上之泵 浦，一面調節稀釋用電解水的供應流量，一面進行電解° 另一方面，如第2圖所示，將電解槽的電解液排出管 路的另一端，接合到已配置在稀釋水流路上之噴射器等的 吸引部，利用稀釋水流來將電解液引進稀釋水中並予以稀 釋之方式的情況下，可以藉由已裝備在稀釋用電解水取出 管路上之節流閥等，來一面調節稀釋用電解水的供應流 量，一面進行電解。 進而，用來解決課題之本發明的第3技術方案’是一 種依照以上所述的方法來生成微酸性電解水之微酸性電解 水生成裝置。 [發明效果] 本發明的效果是在於提供：不會導致裝置的複雜化、 控制上的複雜化，且不必在電解水中添加含有固態物的藥 劑，就可生成具有次氯酸得以穩定存在的pH値範圍之微 200902453 (6) 酸性電解水之方法及裝置。 【實施方式】 爲了要對本發明更深度理解，根據第1圖來說明用來 實施本發明的最佳形態。將與已設置在電解槽4的頂部之 電解液排出口 11相接合之電解液排出管路5的另一端， 接合在稀釋水流路1的中途，將電解液混合在稀釋水中予 以稀釋。在稀釋流路與電解液排出管路之接合部的下游裝 設混合裝置2，以使其完全混合。在混合裝置的下游，接 合鹽酸稀釋用電解水的取出管路9，在鹽酸稀釋用電解水 的取出管路上，裝設稀釋用電解水泵浦1〇。鹽酸供應管 路8連接至鹽酸槽的排出口，另一端則連接至電解槽的鹽 酸供應口 12。在鹽酸供應管路上，裝設鹽酸泵浦7,在該 下游，接合鹽酸稀釋用電解水之取出管路的另一端。 利用這種構成，可以將從鹽酸槽所供應的鹽酸用微酸 性電解水的一部分來稀釋調製過的稀鹽酸予以電解’再以 稀釋水來稀釋以形成微酸性電解水。由於所生成的微酸性 電解水的一部分再度進行電解，故二次性生成之鹽酸的一 部分被電解’ PH値會依該被電解的程度而上升。進而’ 作爲鹽酸稀釋用的水來使用之微酸性電解水’導電度大於 通常的水，因此即使是減少該程度的鹽酸供應量’所生成 之微酸性電解水的PH値仍會升高。 在第1圖所示的裝置中，稀釋水流量設定爲1 000 L / h，使用以硬度200 ppm的硬水所稀釋過之20重量％濃 200902453 (7) 度的鹽酸，在鹽酸稀釋用電解水流量爲400 ml/h，電解 電流爲25 A的狀態下運轉的結果，可獲得有效氯濃度21 ppm、pH値6.1的微酸性電解水1000 L/h。20%鹽酸的 消耗量大約爲95 ml/h。 【圖式簡單說明】 第1圖爲在一面用微酸性電解水的一部分來將鹽酸稀 釋，一面生成微酸性電解水的裝置中，在鹽酸的供應及稀 釋用電解水的供應上，使用泵浦的情況之流程圖。 第2圖爲在一面用微酸性電解水的一部分來將鹽酸稀 釋，一面生成微酸性電解水的裝置中，在稀釋水流路上裝 設噴射器，將電解槽之電解液排出管路的另一端’接合至 已配置在稀釋水流路上之噴射器等的吸引部，以利用稀釋 水流來將電解液引進稀釋水中予以稀釋的方式’利用裝設 在各別的管路上之調節閥，進行鹽酸供應及稀釋用電解水 供應上的控制的方式之流程圖。 【主要元件符號說明】 1 :稀釋水流路 2 :混合器 3 :微酸性電解水出口 4 :電解槽 5 :電解液排出管路 6 :鹽酸槽 -10- 200902453 (8) 7 :鹽酸泵浦 8 :鹽酸供應管路 9:鹽酸稀釋用電解水取出管路 1 〇 :稀釋用電解水泵浦 1 1 :電解液排出口 1 2 :鹽酸供應口 1 3 :噴射器 1 4 :稀釋用電解水流量調節閥 1 5 :鹽酸流量調節閥 -11 -Cl2 + H20 — HOC1 + HC1 ......Chemical Formula 2 Therefore, when the electrolyte is used and the electrolyte is diluted, it will become an abnormally low pH if it does not contain a buffering component in the dilution water.値, and will result in the area where the detached monomeric hypochlorous acid is present. The method of the present patent document 2 is considered to be a disadvantage of the technique disclosed in Japanese Patent Laid-Open No. 1 by the inclusion of the hydrochloric acid in the liquid solution of the electrolysis 200902453 (3), but as a source of chlorine ions. If the amount of salt is increased more than hydrochloric acid, the effect of increasing pH will not be obtained. Therefore, a considerable amount of Na derived from the raw material is contained in the produced electrolyzed water, and the solid matter remains after drying, so that it is extremely inconvenient. In addition, since two kinds of chemicals must be used, it is inevitable that the device is complicated and the control is complicated. On the other hand, in the technique of Japanese Patent Laid-Open No. 3, it is necessary to provide a buffer addition step in the subsequent step of generating electrolyzed water, and it is not possible to avoid complication and enlargement of the apparatus, and it is necessary to confirm pH, etc. in the addition step. Adding a buffer on one side, of course, the control will become complicated. Therefore, predictable devices will be larger and more expensive. In addition, since the buffer to be added is a solution of a solid matter, as in the technique disclosed in Japanese Patent Laid-Open No. 2, there is a risk of causing a disadvantage of depositing a solid after use of electrolyzed water. Accordingly, the problem to be solved by the present invention is to provide a product which does not cause complication of the device and is complicated in control, and it is not necessary to add a drug containing a solid matter to the electrolyzed water to form a hypochlorous acid which is stably present. Method and apparatus for slightly acidic electrolyzed water in the pH range. <Means for Solving the Problem> The reaction caused when hydrochloric acid is diluted with water to form slightly acidic electrolyzed water after electrolysis is the same as Chemical Formula 1 and Chemical Formula 2 described above. At the stage after the dilution, hydrochloric acid containing the same molar concentration as hypochlorous acid is obtained. -6- 200902453 (4) Then, a part of the generated slightly acidic electrolyzed water is again guided to the electrolytic cell and electrolyzed, whereby the final amount of hydrochloric acid can be reduced. In the known electrolysis method of hydrochloric acid, a part of the dilution water is used to dilute a higher concentration of hydrochloric acid while electrolysis is carried out, and the electrolysis is carried out, but of course, the water used for the dilution is changed to be used. The slightly acidic electrolyzed water. According to this method, for example, by controlling the electrolysis current by the conductivity of the electrolyzed liquid, and diluting with slightly acidic electrolyzed water instead of water, the conductivity of the slightly acidic electrolyzed water is lower than that of water (conductivity). The amount of hydrochloric acid used can also be expected to increase as the pH of the slightly acidic electrolyzed water produced increases. Then, the first aspect of the present invention to solve the problem is to electrolyze hydrochloric acid containing an inorganic component other than salt or/and salt, and dilute the generated electrolyte with water using a diaphragmless electrolytic cell to generate In the method of slightly acidic electrolyzed water, diluted hydrochloric acid is used as a electrolytic stock solution using a part of the slightly acidic electrolyzed water produced. Hydrochloric acid containing an inorganic component other than salt or/and salt is contained in an inorganic component of hydrochloric acid itself. For example, an alkali metal or an alkaline earth metal may become an alkaline component by electrolysis and react with a part of hydrochloric acid. Helps to raise the pH 値. The hydrochloric acid is not specifically added with an inorganic component, but is used as a dilution water for diluting hydrochloric acid, for example, water containing an inorganic component such as hard water or deep ocean water, whereby an inorganic component is obtained. Next, the second aspect of the present invention for solving the problem is an operation of diluting hydrochloric acid using the generated slightly acidic electrolyzed water, and an operation of electrolytically diluting 200902453 (5) hydrochloric acid and generating slightly acidic electrolyzed water. , respectively, continuously. In this way, it is possible to continuously generate PH-stabilized slightly acidic electrolyzed water. In order to use a slightly acidic electrolyzed water to dilute hydrochloric acid to one side-surface electrolysis, for example, in a subsequent step of the step of mixing the electrolyte in the dilution water, a take-out line for diluting the electrolyzed water is connected, and the line is connected. The other end is connected to the hydrochloric acid supply flow path. As shown in Fig. 1, the structure of the hydrochloric acid supplied by the pumping can be connected to the hydrochloric acid supply line downstream of the hydrochloric acid supply pump to the dilution electrolysis water take-out line, and is taken out by the electrolysis water for dilution. The pump on the pipeline adjusts the supply flow rate of the diluted electrolyzed water while performing electrolysis. On the other hand, as shown in Fig. 2, the other end of the electrolyte discharge line of the electrolysis cell is joined to the diluted In the case where the suction portion of the ejector or the like on the water flow path is introduced into the dilution water by the dilution water flow and is diluted, the throttle valve or the like which is already provided in the electrolysis water removal line for dilution can be used. Electrolysis was carried out while adjusting the supply flow rate of the electrolyzed water for dilution. Further, a third aspect of the present invention to solve the problem is a slightly acidic electrolyzed water generating apparatus for producing slightly acidic electrolyzed water according to the above method. [Effect of the Invention] The effect of the present invention is to provide a pH which has a stable presence of hypochlorous acid without causing complication of the apparatus and complication of control, and it is not necessary to add a chemical containing solid matter to the electrolyzed water.値Scope of the micro200902453 (6) Method and device for acidic electrolyzed water. [Embodiment] In order to better understand the present invention, the best mode for carrying out the invention will be described based on Fig. 1 . The other end of the electrolytic solution discharge line 5 joined to the electrolytic solution discharge port 11 provided at the top of the electrolytic cell 4 is joined to the middle of the dilution water flow path 1, and the electrolytic solution is mixed in the dilution water to be diluted. The mixing device 2 is installed downstream of the joint portion between the dilution flow path and the electrolyte discharge line to be completely mixed. In the downstream of the mixing device, the extraction line 9 for the electrolyzed water for diluting hydrochloric acid is connected, and the electrolysis water pump for dilution is installed in the extraction line for the electrolyzed water for diluting hydrochloric acid. The hydrochloric acid supply pipe 8 is connected to the discharge port of the hydrochloric acid tank, and the other end is connected to the hydrochloric acid supply port 12 of the electrolytic tank. On the hydrochloric acid supply line, a hydrochloric acid pump 7 is installed, and downstream of this, the other end of the take-out line for electrolyzing water for hydrochloric acid dilution is joined. With this configuration, the hydrochloric acid supplied from the hydrochloric acid tank can be diluted with a part of the slightly acidic electrolyzed water to be electrolyzed and diluted with diluted water to form slightly acidic electrolyzed water. Since a part of the slightly acidic electrolyzed water to be produced is electrolyzed again, a part of the hydrochloric acid which is formed secondaryly is electrolyzed, and PH is increased depending on the degree of electrolysis. Further, since the slightly acidic electrolyzed water used as the water for dilution of hydrochloric acid has a conductivity higher than that of ordinary water, the pH of the slightly acidic electrolyzed water produced by reducing the supply amount of hydrochloric acid to this extent is increased. In the apparatus shown in Fig. 1, the dilution water flow rate is set to 1 000 L / h, and 20% by weight of 200,902,453 (7) degrees of hydrochloric acid diluted with hard water having a hardness of 200 ppm is used, and electrolytic water diluted with hydrochloric acid is used. When the flow rate was 400 ml/h and the electrolysis current was 25 A, the slightly acidic electrolyzed water having an effective chlorine concentration of 21 ppm and a pH of 6.1 was obtained at 1000 L/h. The consumption of 20% hydrochloric acid is approximately 95 ml/h. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the use of a pump for the supply of hydrochloric acid and the supply of electrolyzed water for dilution in a device for producing slightly acidic electrolyzed water by diluting hydrochloric acid with a part of slightly acidic electrolyzed water. Flow chart of the situation. Fig. 2 is a view showing an apparatus for producing a slightly acidic electrolyzed water by diluting hydrochloric acid with a part of slightly acidic electrolyzed water on one side, and installing an ejector on the dilution water flow path to discharge the electrolyte of the electrolytic cell to the other end of the pipe. A suction portion that is joined to an ejector or the like that has been disposed on a flow path of a dilution water, and a method of diluting the electrolyte into a dilution water by a dilution water flow, and using a regulating valve installed in each of the pipes to supply and dilute hydrochloric acid A flow chart of the manner in which the control on the supply of electrolyzed water is used. [Explanation of main component symbols] 1: Diluted water flow path 2: Mixer 3: slightly acidic electrolyzed water outlet 4: Electrolytic cell 5: Electrolyte discharge line 6: Hydrochloric acid tank-10-200902453 (8) 7: Hydrochloric acid pump 8 : Hydrochloric acid supply line 9: Hydrochloric acid dilution with electrolytic water to take out the line 1 〇: Electrolytic water pump for dilution 1 1 : Electrolyte discharge port 1 2: Hydrochloric acid supply port 1 3 : Injector 1 4 : Dilution electrolyzed water flow Regulating valve 1 5 : Hydrochloric acid flow regulating valve -11 -