1244466 五、發明説明（3 ) 逆滲透膜裝置由逆滲透膜兀件、耐應荇器、加壓泵等 組成。饋入此逆滲透膜裝置的被處理液通常加入殺菌 劑、凝結劑、還原劑、p Η調節劑等藥液，經過凝結、 沈澱、砂濾、離子過濾（ρ 0 1 i S h i n g )、活性碳過濾、精 密過濾、超過濾、安全過濾器等前處理後，再饋入裝 置。例如進行海水脫鹽時，採取海水後在沈澱池分離顆 粒，並在此添加氯等殺菌劑以殺菌。其次添加氯化鐵、 聚氯化鋁等凝結劑進行砂過濾。濾液儲存在儲槽，以硫 酸等調節pH後再運送。運送中添加亞硫酸氫鈉等還 原劑以還原去除殺菌劑，使通過安全過濾器後以高壓泵 使此液體昇壓，饋入逆滲透膜組件。惟這些前處理可依 被處理液的種類、用途作適當的選擇。 逆滲透膜是指一種可讓溶液中的一部分成分例如溶 劑等穿透，而其他成分無法穿透的半透性膜。包括毫微 濾膜及逆滲透膜等。· ·般常用的逆滲透膜的材料例如 醋酸纖維素類聚合物、聚醯胺、聚酯、聚醯亞胺、乙 烯聚合物等高分子材料。其結構例如非對稱膜和複合 膜等，非對稱膜係在膜的至少單側含有緻密層，具有一 種細微孔其孔徑從此緻密層往膜內部或另一側逐漸變 大，而複合膜係在此非對稱膜的緻密膜之上方具有由其 他材料形成的非常薄的活性層-組成膜的物質例如中 空結構、平膜等。通常J f I空結構及平膜的膜厚爲1 0 m 〜1 mm ,中空結構的外徑爲5 Ο # m〜4 imii。以平膜負載在 非對稱膜，複合膜負載在編織物、不織布等基材上較理 1244466 五、發明説明（4 ) 想。但本發明的方法不受逆滲膜的材料、膜構造、或 組成膜的材料之型態影響（中空結構或平膜），皆可使用 且具有效果。 具代表性的逆滲透膜，例如醋酸纖維素類或聚醯胺類 的非對稱膜，含有聚醯胺類、聚尿素類的活性層之複合 膜等。本發明的方法尤其在其中醋酸纖維素類的非對 稱膜、聚醯胺類的複合膜特別有效。又以芳香族類的 聚醯胺複合膜具有更佳的效果。 逆滲透膜組件是指爲了使上述逆滲透膜能實際應用， 而加以形狀化的物質。以平膜爲例可以使成螺旋，管型 或板式-框架等形狀。而中空結構可使成爲在上方成束 的組件來使用。本發明不受這些滲逆透膜組件的組成 型態影響皆適用。 逆滲透膜組件爲螺旋形狀時，組入被處理液的流路材 料、滲透液的流路材料等部分。這些部分若使用用於 筒濃度、局壓用的流路材料，則本發明的效果更佳。 逆滲透膜裝置的運轉壓力通常在O.IMPa〜15aMP的 範圍，依被處理液的種類、運轉方法等適切地作使用區 別。以鹹水等低滲透壓的溶液爲被處理液時，使用較低 的壓力，而以海水和工業廢水等爲處理液時使用較高的 壓力。 逆滲透膜裝置的運轉溫度在0 °C〜1 0 0 °C的範圍較理 想。低於〇 °C時恐有被處理液受凍結之虞，高於1 〇 〇。〇 時則可能導致被處理液的蒸發。 -6- 1244466 五、發明説明（5 ) 在逆滲透膜裝置中的被處理液之回收率通常可在 5〜98%間作適當的選擇。惟必須依被處理液和濃縮液 的性狀、濃度、滲透壓等，而考慮前處理的方法和運轉 壓力再設定回收率。例如，進行海水淡化時通常設定 10〜4 0%的回收率，若爲高效率的裝置則設定40〜70%的 回收率。進行鹹水淡化或製造超純水時通常設定爲 7 0 %以上，必要時可以90〜95 %的高回收率進行運轉。回 收率是指穿透滲透膜的液量除以被處理液量再乘以 1 〇 0之値。 逆滲透膜裝置主要由高壓泵和逆滲透膜組件構成。 高壓泵可依裝置的運轉壓力選擇最適當的泵。 逆滲透膜組件的配列可以只使用1段，但以相對於被 處理液直列、並列多段配列的方式較理想。以直列的 方式配列時，可在逆滲透膜組件之間設置升壓泵。進行 海水淡化時從裝置成本考量，特別以直列2段的配置方 式較理想。此時在配列成直列的組件之間設置升壓泵， 使被處理液升壓至1 .0〜5.0 M Pa，再饋入後段的組件較理 想。對被處理液而言以直列的方式配列時，因爲膜組件 和被處理液接觸的時間長，故本發明的效果大。 又，逆滲透膜組件亦可採用相對於滲透液爲直列的配 列方式。此法適用於當滲透液的品質不佳或欲回收滲 透液中的溶質成分時。將逆滲透膜組件配列成對於滲 透液爲直列時，在逆滲透膜組件間設置泵，再對滲透液 加壓或先在前段即加足壓力，再利用爲後段的壓力以進 1244466 ; 五、發明説明（6 ) 行 膜 分 離 較 理想。又，將逆滲膜組件配列成對於滲透液 爲 直 列 時 ，爲了進行後面的逆滲透膜組件之殺菌，將添 加 酸 的 裝 置 設置在逆滲透膜組件和逆滲透膜組件之間 較 理 想 〇 在 逆 滲 透 膜裝置中，無法穿透內膜的被處理液部份當 成 濃 縮 液 ，從膜組件中取出。此濃縮液可再利用、丟棄 或 以 其 他 方 法濃縮。又，濃縮液的一部分或全部亦可在 被 處 理 液 中 循環。已穿透膜的滲透液可再利用或丟棄， 其 — 部 分 或 全部亦可在被處理液中循環。 通 常 逆 滲 透膜裝置的濃縮液具有壓力能量爲了降 低 運 轉 成 本 ，回收此能量較理想。回收能量的方法，可 利 用 附 設 在 任一部分的高壓泵之能量回收裝置進行回 收 ，但以 :m 1設 :在高壓泵前後，或組件之間的專用渦輪式 能 量 回 收 泵 進行回收較適當。本發明使用的膜分離裝 置 之 處 理 能 力，以一日的處理水量爲0.5m3〜100萬m3 的 裝 置 較 適 當。 在 本 發 明 使用的膜分離裝置中，裝置內的配管以少滯 留 部 份 之 結 構較理想。 本 發 明 的 水處理方法在饋入水處理裝置的被處理液 中 添 加 酸 及 防蝕劑。添加酸在提供殺菌效果方面非常 重 要 ，特 :別 [是 :在以海水爲被處理液的膜過濾中此效果顯 著 〇 微 生 物 的死滅pH値依微生物種而異，例如大腸菌 的 生 存 下 限 pH値爲4.6,在ρΗ3·4以下會死亡。有許多 種 微 生 物 生 存在海水中，各個的死減pH値均不同。通 -8- 1244466 五、發明説明（7 ) 常將海水維持在ρΗ4·0以下一段時間後，50〜100%的微 生物會死亡。添加酸及防蝕劑的被處理液之pH在3.9 以下較理想，又以3.7以下更佳，3 ·4以下特別適當。沒 有特別限制ρ Η値的下限，但從預防裝置被腐蝕的觀點 考量，以1 .5以上較理想，特別以2.0以上更佳。 通常使用酸以達到期望的pH狀態。可使用任一種 有機酸或無機酸，惟從經濟面考量使用硫酸較適當。 本發明使用的防蝕劑對預防水處理裝置被腐蝕、提 高殺菌結果而言是重要的。本發明使用的防蝕劑，以選 自分子中至少有6個羧酸基的聚羧酸、乙二胺四乙 酸、亞硝酸及其鹼金屬鹽者較適當。較理想的聚羧酸 係至少一種選自下述一般式（式中η爲3以上的整 數，X、Υ爲氫或鹼金屬）表示的聚環氧琥珀酸、聚丙烯 酸、聚馬來酸及馬來酸共聚物等化合物。 HO一一 CH-CH—0--Η L Jn1244466 V. Description of the invention (3) The reverse osmosis membrane device is composed of a reverse osmosis membrane element, a pressure resistant device, a pressure pump, and the like. The liquid to be fed into the reverse osmosis membrane device is usually added with chemical liquids such as bactericides, coagulants, reducing agents, p Η regulators, etc., and undergoes coagulation, precipitation, sand filtration, ion filtration (ρ 0 1 i S hing), activity Carbon filter, precision filter, ultra filter, safety filter and other pre-treatment before feeding into the device. For example, when desalination of seawater, after the seawater is taken, the particles are separated in the Shendian pond, and bactericides such as chlorine are added here to sterilize. Next, coagulants such as ferric chloride and polyaluminum chloride are added for sand filtration. The filtrate is stored in a storage tank, and the pH is adjusted with sulfuric acid or the like before being transported. A reducing agent such as sodium bisulfite is added during transportation to reduce and remove the bactericide. After passing through the safety filter, the liquid is pressurized by a high-pressure pump to feed the liquid to the reverse osmosis membrane module. However, these pretreatments can be appropriately selected according to the type and application of the liquid to be treated. A reverse osmosis membrane is a semi-permeable membrane that allows some of the components in a solution, such as a solvent, to penetrate, but not others. Including nanofiltration membranes and reverse osmosis membranes. · Commonly used materials for reverse osmosis membranes, such as polymer materials such as cellulose acetate polymers, polyamides, polyesters, polyimides, and ethylene polymers. Its structure such as asymmetric membrane and composite membrane, asymmetric membrane system contains a dense layer on at least one side of the membrane, has a kind of fine pores, and its pore diameter gradually increases from the dense layer to the inside or the other side of the membrane, and the composite membrane system Above the dense film of this asymmetric film, there are very thin active layer-materials that make up the film, such as hollow structures, flat films, etc., formed of other materials. Generally, the film thickness of J f I hollow structure and flat film is 10 m ~ 1 mm, and the outer diameter of hollow structure is 5 0 # m ~ 4 imii. It is reasonable to load flat film on asymmetric film, and composite film on woven fabrics, non-woven fabrics and other substrates. 1244466 V. Description of the invention (4). However, the method of the present invention is not affected by the material of the reverse osmosis membrane, the structure of the membrane, or the type of the material constituting the membrane (hollow structure or flat membrane), and can be used and has an effect. Typical reverse osmosis membranes include, for example, asymmetric membranes of cellulose acetate or polyamines, and composite membranes containing polyamines and polyurea-based active layers. The method of the present invention is particularly effective in asymmetric membranes of cellulose acetate and composite membranes of polyamide. Aromatic polyamide-based composite film has better effect. The reverse osmosis membrane module refers to a material that is shaped so that the above reverse osmosis membrane can be practically applied. Taking flat film as an example, it can be formed into spiral, tube or plate-frame. The hollow structure can be used as a bundle above. The present invention is applicable regardless of the composition type of these reverse osmosis membrane modules. When the reverse osmosis membrane module has a spiral shape, the flow path material of the liquid to be treated and the flow path material of the permeate liquid are incorporated. The effect of the present invention is better when a flow path material for cylinder concentration and partial pressure is used for these parts. The operating pressure of the reverse osmosis membrane device is usually in the range of 0.1 MPa to 15 aMP, and it is appropriately used according to the type of the liquid to be treated and the operation method. When a solution with low osmotic pressure such as salt water is used as the liquid to be treated, a lower pressure is used, and when a solution such as seawater or industrial wastewater is used as a treatment liquid, a higher pressure is used. The operating temperature of the reverse osmosis membrane device is preferably in the range of 0 ° C to 100 ° C. When the temperature is lower than 0 ° C, the treated liquid may be frozen, which is higher than 100. ○ hour may cause evaporation of the treated liquid. -6- 1244466 V. Description of the invention (5) The recovery rate of the treated liquid in the reverse osmosis membrane device can usually be appropriately selected between 5 ~ 98%. However, the recovery rate must be set based on the properties, concentration, and osmotic pressure of the treated liquid and concentrated liquid, taking into account the pretreatment method and operating pressure. For example, when desalination is performed, a recovery rate of 10 to 40% is usually set, and for a high-efficiency device, a recovery rate of 40 to 70% is set. When desalinating salt water or making ultrapure water, it is usually set to 70% or more, and it can be operated with a high recovery rate of 90 to 95% when necessary. The recovery rate refers to the amount of liquid penetrating the permeable membrane divided by the amount of liquid to be treated and then multiplied by 1,000. The reverse osmosis membrane device is mainly composed of a high-pressure pump and a reverse osmosis membrane module. The high-pressure pump can choose the most appropriate pump according to the operating pressure of the device. The arrangement of the reverse osmosis membrane module may use only one stage. However, it is preferable to arrange the reverse osmosis membrane module in parallel with a plurality of stages. When arranged in an in-line manner, a booster pump can be installed between the reverse osmosis membrane modules. Considering the cost of the device when desalination is carried out, it is particularly desirable to use an in-line two-stage arrangement. At this time, a booster pump is set between the components arranged in line to boost the liquid to be treated to 1.0 ~ 5.0 M Pa, and it is more ideal to feed the components in the later stage. When the liquid to be processed is arranged in an in-line manner, the effect of the present invention is great because the contact time between the membrane module and the liquid to be processed is long. In addition, the reverse osmosis membrane module may be arranged in line with the permeate. This method is applicable when the quality of the permeate is not good or when the solute component in the permeate is to be recovered. When the reverse osmosis membrane module is arranged in line with the permeate, a pump is installed between the reverse osmosis membrane modules, and then the permeate is pressurized or the pressure is first applied to the front section, and then the pressure is used as the rear section to enter 1244466; Description of the invention (6) Membrane separation is ideal. In addition, when the reverse osmosis membrane module is arranged in line with the permeate, in order to sterilize the subsequent reverse osmosis membrane module, it is desirable to install a device for adding an acid between the reverse osmosis membrane module and the reverse osmosis membrane module. In the osmotic membrane device, the part of the liquid to be treated that cannot penetrate the inner membrane is regarded as a concentrated liquid and taken out from the membrane module. This concentrate can be reused, discarded, or concentrated by other methods. In addition, part or all of the concentrated liquid may be circulated in the liquid to be treated. The permeate that has penetrated the membrane can be reused or discarded, and some or all of it can be circulated in the liquid to be treated. Generally, the concentrated liquid of the reverse osmosis membrane device has pressure energy. In order to reduce the operating cost, it is ideal to recover this energy. The method of energy recovery can be recovered by using the energy recovery device of the high-pressure pump attached to any part, but it is more appropriate to use: m 1: special turbo-type energy recovery pumps located before and after the high-pressure pump or between components. The processing capability of the membrane separation device used in the present invention is suitable for a device that can treat 0.5 to 3 million m3 of water per day. In the membrane separation device used in the present invention, it is preferable that the piping in the device has a structure with less retention. The water treatment method of the present invention adds an acid and an anticorrosive agent to the liquid to be treated fed to the water treatment device. The addition of acid is very important in providing bactericidal effects, especially: Do n’t [Yes: This effect is significant in membrane filtration using seawater as the treated liquid. The death pH of microorganisms varies according to the species of microorganisms, such as the lower limit of coliform pH 値. 4.6, will die below ρΗ3.4. There are many kinds of microorganisms living in seawater, each of which has a different pH value.通 -8- 1244466 V. Description of the invention (7) After keeping the seawater below ρΗ4.0 for a period of time, 50 ~ 100% of the microorganisms will die. The pH of the treated liquid to which an acid and an anticorrosive agent are added is preferably below 3.9, more preferably below 3.7, and particularly preferably below 3.4. There is no particular limitation on the lower limit of ρ Η 値, but from the viewpoint of preventing corrosion of the device, it is preferably 1.5 or more, and more preferably 2.0 or more. Acid is usually used to achieve the desired pH state. Either organic or inorganic acids can be used, but sulfuric acid is more economically appropriate. The anticorrosive agent used in the present invention is important for preventing the water treatment device from being corroded and improving the sterilization result. The anticorrosive agent used in the present invention is suitably selected from polycarboxylic acid, ethylenediaminetetraacetic acid, nitrous acid and alkali metal salts thereof having at least 6 carboxylic acid groups in the molecule. More preferably, at least one type of polycarboxylic acid is selected from the group consisting of polyepoxysuccinic acid, polyacrylic acid, polymaleic acid, and Maleic acid copolymers and other compounds. HO one one CH-CH—0--Η L Jn
COOX COOY 特別理想的防蝕劑係選自聚環氧琥珀酸、乙二胺四 乙酸、聚丙烯酸及其鹼金屬鹽等化合物。這些化合物 因爲分子中含有氧、氮等陰電度大的原子，在金屬表面 的吸附性佳較理想。 聚環氧琥珀酸及其鹼金屬鹽以下列的方法合成。亦 即，以鎢酸鈉爲觸媒，利用過氧化氫使馬來酸鹽環氧化， -9- 1244466 五、發明説明（1G) 化。又，水處理用殺菌劑的添加量多於1 〇重量％時會增 加水處理用殺菌劑的添加裝置之負荷，增加能量的消費 量，故不利於經濟面的考量。 例如，使用pHO.5、防蝕劑濃度爲0.1重量％的水處 理用殺菌劑，使被處理液的pH成爲2.5時，約添加1重 量％的水處理用殺菌劑。 本發明的水處理方法，酸和防蝕劑也可以個別加入被 處理液中。酸在被處理液中的添加量從殺菌效果的觀 點考量，多於1 0 p p m (重量）較適當，從經濟面和預防配管 等設備腐蝕觀點考量，少於1重量％較理想。 使用硫酸時其添加量和被處理液的鹽濃度成比例較 理想。例如經過加壓滅菌（120 °C、15分鐘）的生理食鹽 水（食鹽濃度0.9重量％)中添加硫酸50ppm可使pH値 下降至3.2，但以經過加壓滅菌（1 2 (TC、1 5分鐘）的3處 海水及市面販售的人工海水（鹽濃度約3.5重量％)使用 爲被處理液時，即使添加1 0 0 p p m的硫酸被處理液的P Η 値仍在5.0〜5.8間◦這主要是受海水的Μ鹼度的影 響。爲了使海水的pH値降至4以下通常較理想的做 法是添加1 2 0 p p m (重量）以上的硫酸。從經濟面和預防 配管寺设備腐餓的觀點考量，硫酸添加量的上限在 4 0 0ppm以下較理想，以3 0 0ppm以下更佳。在上述的海 水、人工海水中添加硫酸的濃度爲150ppm、200ppm 時，其口11値分別爲卩113.2〜3.6、卩112.8〜2.9。亦即，隨者 硫酸添加濃度的增加，處理液的p Η不規則性會減少。 -12- 1244466 五、發明説明（11 ) 被處理液中防蝕劑濃度的最適範圍依被處理液的種 類和水處理條件而變化，通常在〇 . 1 Ρ Ρ Π1 (重量）〜1重量％ 的範圍較理想。從經濟面和水處理操作的簡便性考量， 在1〜5 0 0 p p m的範圍內更適當◦例如，ρ Η 1 . 0、鹽濃度 約8 %的廢水於3 5 t進行水處理時.防蝕劑在被處理液 中的範圍以1〜1 〇 〇 P P m爲佳。 本發明中酸及防飩劑不限制添加的位置，只要在被處 理液饋入膜分離裝置之前的：]::程中添加即可。爲了膜 分離裝置的殺菌膜分離裝置前一步驟添加較理想。進 行水處理的同時也進行殺菌處理較理想，亦可在停止時 .(% 進殺菌處理。 間歇性地添加酸及防飩劑較理想。每次的添加時間 約在0.5〜2.5小時的範圍內較佳，添加頻率爲1天〜1個 月1次較適當。可依穿透膜水量的變動、濃縮液的生 菌數和有機碳的變動、膜壓的上昇等，適當地改變添加 時間和添加頻率較理想。至於膜的除菌，可在水處理裝 置停止時將膜浸漬在含有酸及防蝕劑的水溶液中。 分開添加酸及防蝕劑時，亦可改變個別的添加頻率。 例如酸隔日添加〇 . 5〜2 . 5小時.而防蝕劑1週添加1次 且和酸相_時間。特別是在防蝕劑昂貴而其防蝕效果 足夠時，從經濟的觀點考量，以減少防蝕劑的添加頻率 而只添加酸同時添加酸及防蝕劑等做法組合搭配較適 當。 具有本發明的膜分離裝置之水處理裝置，係例如由下 -13- 1244466 五、發明説明（12) 列表不的A〜Η所組成的裝置。 A ·取水裝置。收取被裝置液（原水）的裝置，通常由取水 泵、藥品導入設備等組成。 B·貫通取水裝置的前處理裝置。使饋入分離膜裝置的 被處理液經過前處理，去除被處理液中的懸浮物、乳 化物等，饋入一部分藥劑之裝置。例如可依下列的順 序組成。 B -1凝結過濾、裝置 B-2離子交換過濾裝置 亦可使用超濾裝置和精密過濾裝置取代B-1、B-2。 B - 3饋入凝結劑、殺菌劑、ρ η調節劑等藥劑的設備。 C .依需求設備貫通前處理裝置的中間槽。具有水量調 節、水質緩衝作用的功能。 D.設置C時貫通中間槽，或不設置c時貫通前處理裝置 的過濾器。 去除饋入膜分離裝置的被處理液之固態雜質。 Ε·膜分離裝置。由高壓泵及分離膜組件構成。 設置多數個膜分膜裝置，這些可設置爲並排或直排。設 置成直排時，可以在膜分離裝置間設置泵，此泵可增加 在後段的分離膜裝置饋入被處理液時的水壓。 F .貫通膜的分離裝置的滲透液出口部份的後處理裝 置。例如下列表示的裝置。 F-1脫氣裝置。具有脫碳酸的功能。 F - 2鈣塔。 -14- 1244466 五、發明説明（14) 本發明的水處理方法適用於使用膜分離裝置的水處 理。特別適用於海水的淡化、鹹水的淡化、工業用水的 製造、超純水和純水的製造、醫藥用純水的製造、自 來水原水的除濁、自來水的高度處理等水的精製工 程。又，在食品的濃縮等方面，分離或濃縮容易被以前 的氧化性殺菌劑解離的有機物時，可在不解離的情況下 濃縮或回收此有機物，本發明的效果顯著。製造飮料時 可預防因氯殺菌產生的三鹵甲烷發生。本發明的水處 理方法在由海水產生之菌的殺菌處理特別有效。 通常添加氯殺菌劑對殺菌有效。當水處理裝置具有 膜分離裝置時，例如在上述A〜D的裝置中任一工程，進 行連續或間歇性注入氯殺菌劑。根據此法，饋入的被處 理液只要未出現耐性菌，幾乎能完全殺菌。爲了防止因 氯殺菌劑使逆滲透膜發生劣化，通常在膜分離裝置的前 一步驟添加以亞硫酸氫鈉爲代表的還原劑。但是，因還 原劑而還原去除氯後的被處理液，微生物容易在其中繁 殖。而且不像添加殺菌劑前的海水原水般有各種微生 物，而是經特別篩選的微生物群存在其中，當中可能含 有多數的耐酸性菌。間歇性地分別在前處理工程添加 氯殺菌劑和在膜分離裝置前一步驟注入還原劑可解決 此問題。此法對預防膜發生劣化也有效。氯殺菌劑的 注入間隔，例如配合海水原水的水質即微生物的生存狀 況，1日〜6個月進行1次、1次3 0分〜2小時較理想。 配合此氯殺菌劑的添加時機，並考慮含氯殺菌劑的水的 -16- 1244466 五、發明説明（15 ) 移動，在前處理裝置和膜分離裝置間饋入還原劑使 菌劑非活性化較適當。又，配合此時機在饋入膜分 置的水溶液中個別添加本發明的水處理用殺菌劑ί 蝕劑及酸，以進行膜的分離裝置的殺菌較理想。 如此，在前處理工程間歇性地注入氯殺菌劑的方 連續地注入殺菌劑的方法比較，在降低藥品費等處 方面具有顯著的效果，使用本發明的水處理用殺菌 酸和防蝕劑的水處理方法，才能首次達到如此的效 以前的殺菌方法因爲殺菌效果不佳無法達成。 實例 在合成例、實例中具體地說明本發明，惟本發明 這些實例限制。首先說明實例中使用的藥液等的-成。 <聚環氧琥珀酸鹽的合成例> 根據 payne 們（J.Org.Chem·，24,54(1959))的合成 以下列的步驟合成聚環氧琥珀酸鹽。 在2 L的三口燒瓶中放入馬來酸酐2 8 0 g及超純 4 2 8 m 1使溶解。在冷卻並維持在室溫的情形下，將 量％氫氧化鉀水溶液5 0 0 g以滴液漏斗滴入上述水 中。其次，加入鎢酸鈉1 8 · 8 g後滴入3 5重量％過氧 水3 3 2 g。攪拌3 0分鐘後緩慢地添加4 8重量％氫 鉀水溶液1 1 5 g。此時急速冷卻燒瓶使反應溫度維 5 5〜6 5 °C。之後的3 0分鐘維持在6 5〜6 0。(：，製得環 珀酸鉀水溶液。冷卻至室溫後，將此水溶液濃縮成 氯殺 離裝 获防 法和 理費 劑或 果， 不受 ，法， 水 48重 溶液 ,化氫 氧化 持在 氧琥 -17- 1244466 五、發明説明（16) 3 0 0 m 1並注入1 L的内酮中，過、臆産7l·:的沈殿物單離 出環氧琥珀酸鉀。 其次在2 0 0 m 1圓底燒瓶中放人此環氧琥珀酸鉀 1 0.4 g和超純水5 0 g，添加4 8重量％的氫氧化鉀，調整水 溶液的pH値爲10.3。再添加氬氧化鉀〇 . 4 1 g，在8 0 °C 下進行反應6小時。接著，冷卻至室溫後過濾不溶物質， 使用旋轉式蒸發器以4 0 °C的浴溫去除水，製得白色的固 態物。 利用凝膠滲透色譜法（G P C )測定製得的聚環氧琥珀 酸鹽之分子量。具體地說，調配2 0 0 PPm的試驗品.使用 分子量已知的聚乙二醇當作標準物質做出檢量線，再計 算試驗品的分子量。製得的聚環氧琥珀酸鹽的分子量， 重量平均分子量 Mw = 20900(n=100，Ww/Mn=1.00)〇 實例1〜3 在純水（導電度1 〇 V s / c m )中加入硫酸2 0 w t %及表1 表不的防蝕劑0.1 wt%，調製水處理用殺菌劑（pHO. 6)。 表面經過3 2 0號的銼刀硏磨處理的S U S 3 1 6 L製不銹鋼 試驗片（2 0誦X 3 0丨uni X 1 nil丨丨），使丨|」超音波洗淨器以純水 淸洗6 0分鐘後以W _淸冼6 0分鐘再風乾。以海水（導 電度1 0 0 m S / c m ) 1 0 0倍稀釋上述水處理用殺菌劑（殺菌 劑濃度1重量％ )，使成總量爲1 〇 〇 ni L的試驗液（ρ Η 1 . 2 ) 並放入1 0 0 m L的聚容器内，將上述不銹鋼試驗片1個1 個地浸漬在其中。準備1 〇個此聚容器靜置在8 0 °C的 溫室內。開始浸漬後的第4 | |和第7日取出試驗厂Γ 測定其重量。試驗片以純水淸冼5秒鐘後再以丙削洗 -18- 1244466 五、發明説明（17 ) 淸5秒鐘，風乾後在矽膠乾燥的環境中使用可彳平量至 〇 · 0 1 m g的電子天坪測定其重量，求5根的平均値。因添 加防蝕劑所產生的效果評估如下： 從開始浸漬到第4日止的減少重量（a)，和從第4日 到弟7日止的減少重量（b)分別根據下列的方法求得。 減少重量（a)(g/m2) = (浸漬前的試驗片重量-第4日的試 驗片重量）/試驗片表面積 減少重量（b)(g/m2) = (第4日的試驗片重量-第7日的試 驗片重量）/試驗片表面積 其次，根據下列的方法個別求出上述減少重量（a)、（ b) 中，使用防蝕劑時的減少重量對不使用防蝕劑時的減少 重量之比。 減少重量（a)比=含防鈾劑的減少重量（a)/不含防蝕劑的 減少重量（a) 減少重量（b )比=含防蝕劑的減少重量（b ) /不含防蝕劑的 減少重量（b ) 減少重量U)比和（b)比的平均値當成重量減少率，結 果如表1所示。 (表中，聚環氧琥珀酸鉀鹽簡寫爲PES、乙二胺四乙 酸四鈉簡寫爲EDTA、聚丙烯酸簡寫爲pa。） 比較例1 ， 除了不添加防蝕劑之外，進行和實例1相同的實驗。 結果如表1所示。不添加防蝕劑之本比較例和實例 1〜3比較，重量減少率大表示試驗片會腐蝕。 -19- 1244466 五、發明説明（18) 表1 防蝕劑 重量減少率 — 實施例1 PES 0.37 實施例2 EDT A 0.58 實施例3 PA 0.67 比較例1 钲 j\\\ 1.00 實例4〜6 在添加硫酸且pH値調爲1的海水（導電度1 OOmS/cm) 中加入表2所示的防蝕劑l〇ppm調製成試驗液。表面 經過3 20號的銼刀硏磨處理的sus 3 04製不銹鋼試驗片 (20醒x3 0 mm xl腿），使用超音波洗淨器以純水淸洗6〇 分鐘後以丙酮洗淸60分鐘再風乾。在i〇〇ml的聚容器 內放入上述試驗液1 0 0 m 1，將上述不銹鋼試驗片1個1 個地浸漬在其中。準備5個此聚容器在3 5 °C的恆溫室 內F#置3日，昇溫至8 0 C後繼續靜置1 7小時。取出試 驗片以純水淸洗3 0秒鐘後再以丙酮淸洗1 〇秒鐘。根 據下列方法測定因腐飩減少的重量。採用5個試驗品 的平均値作爲減少的重量。 減少重量（g/m2) = (浸淸前的試驗片重量-浸漬3日後的 試驗片重量）/試驗片表面積 結果如表2所示。 (表中，聚環氧琥拍酸鉀鹽簡寫爲PES、乙二胺四乙酸四 鈉簡寫爲EDTA、丁烷四羧酸簡寫爲bTC。） 比較例2、3 除了改變表2所示的防蝕劑之外，進行和實例4相同 -20- 1244466 五、發明説明（19 ) 的實驗。 從表2可知，在p Η値爲1的酸性條件下，添力日P E S、 E D T A、聚丙烯酸等防蝕劑的實例，和不添力卩防蝕劑的 比較例2、添加有機羧酸的丁烷四羧酸的比較例3進 行比較，結果具有較佳的防蝕效果。 表2 防蝕劑 濃度（ppm) 重量減少 (g/m2) 實施例4 PES 10 0.19 實施例5 EDT A 10 0.14 實施例6 PA 10 0.3 8 比較例2 Μ - 27.9 比較例3 BTC 10 17.9 實例7、8 在添加硫酸且pH値調爲2.5的海水（導電度 9 8 m S / c m )中加入表3所示的防触劑1 〇 p p m調製成試驗 液。表面經過2 4 0號的銼刀硏磨處理的S u S 3 0 4製不 銹鋼試驗片（1 5 mm X 2 0 mm X 1 mm )，使用超音波洗淨器以 純水淸洗3 0分鐘後以丙酮洗淸3 0分鐘再風乾。在 1 0 0 m L的聚谷益內放入上述試驗液1 〇 〇 m 1，將上述不_ 鋼試驗片1個1個地浸漬在其中。準備5個此聚容器 在3 5 °C的恆溫室內靜置8日，取出試驗片以純水淸洗 3 0秒鐘再以丙酮淸洗1 〇秒鐘。依實例4相同的方法 來測定因腐蝕減少的重量。其結果如表3所示。 (表中亞硝酸鈉簡寫爲NaN02) 比較例4 -21- 1244466 五、發明説明（2〇) 除了不添加防蝕劑之外，進行和實例7相同的實驗。 結果如表3所不。不添加防飩劑的本例，試驗片減少較 多的重量。 表3 ·· 防蝕劑 濃度（ppm) 重量減少 (g/m2) 實施例7 NaN02 10 14.2 實施例8 EDT A 10 9.8 比較例4 並 > \ N\ - 23.5 實例9、1 0 在添加硫酸且Ρ Η値調爲1的海水（導電度1 0 〇 m S / c m ) 中加入表4所示的防蝕劑1 0 p p m調製成試驗液。表面 經過3 2 0號的銼刀硏磨處理的S U S 3 0 4及S U S 3 1 6製不 銹鋼試驗片（2 0 mm X 3 0醒]X 1 min )，使用超音波洗淨器以 純水淸洗6 0分鐘後以丙酮洗淸6 0分鐘再風乾。在 lOOmL的聚容器內放入上述試驗液100ml，將上述不銹 鋼試驗片1個1個地浸漬在其中。準備1 〇個此聚容器 在8 0 °C的恆溫室內靜置4 |:1，取出試驗片以純水淸洗5 秒鐘再以丙酮淸洗5秒鐘。依實例4相N的方法來測 定因腐蝕減少的重景。其結果如表4所不。 (表中，聚環氧琥珀酸鉀鹽簡寫爲PES、馬來酸烯烴共聚 物的鈉鹽簡寫爲Ρ Μ 0。） 比較例5 除Γ不添加防蝕劑之外，進行和實例9相同的實驗。 結果如表4所示。不添加防蝕劑的木例，試驗片減少較 -22- 1244466 五、發明説明（21 ) 多的重量。 表4 防鈾劑 》辰度（p p m ) 重量減少（g/m2) SUS304 SUS316 實施例9 實施例1 〇 PES 10 0.0833 7.71 PMO 10 36.1 8.35 比較例5 - 43.7 23.7 實例1 1、1 2、參考例1 鹽濃度5 · 8重量％的海水在3 〇 °C下靜置一晚，使生菌 數安定後以滅菌水稀釋成3 . 5重量％ (稱爲A液）。A液 pH的値爲6 · 6。在已添加表5的防蝕劑1重量％之海 水（導電度98.5mS/cm)中加入上述A液1重量％，再添 加硫酸使pH爲3.0,在3 (TC下靜置30分鐘（稱爲B 液）。測定B液的生菌數。生菌數的測定則使用 1/20RI培養基（測定海洋性細菌用培養基），在3〇°C下培 養6日後數算出現的群落，以生菌數殘存率表示相對於 不調節p Η時（A液）的生菌數，亦即，以下列的式子求出 菌數殘存率（％ )。 生菌數殘存率（％H反應後（B液）的生菌數）/(不調節pH 時（A液）的生菌數）X 1 〇 〇 結果如表5所示。從表5可知即使添加PES、EDTA, 對硫酸之殺菌效果產生不良的影響，仍可維持優良的殺 菌效果。其中參考例係不添加防蝕劑，其殺菌效果雖佳 但不具防蝕效果。 比較例6〜8 -23- 1244466 五、發明説明（22 ) 除了改變B液的p Η値爲7.2或6 · 6之外進行和實例 1 1相同的實驗。結果如表5所示。β液的ρ Η値較高 的這些比較例 表5 不具殺菌效果 〇 防蝕劑 PH 生菌殘存 (%) 實施例1 1 PES 3.0 0.07 〜 實施例1 2 EDT A 3.0 0.5 ~~^ 參考例1 無 3.0 0.05 比較例6 PES 7.2 39.5 比較例7 EDTA 7.2 24.1 ~ 比較例8 無 6.6 ---- 39.6 實例1 3、1 4、 比較例9 - ----1 在純水（導電度1 0 // S/cm)中添加硫酸20wt%、表6 表示的防蝕劑0 · 1 wt%調製水處理裝置的殺菌劑。實例 1 3則再添加保存穩疋劑的棒檬酸鈉及蘋果酸各爲〇. $ 重量°/。。表面經過3 2 0號的銼刀硏磨處理的s u S 3 0 4製 不銹鋼試片 （2 〇 111111 x 3 〇 cm X 1 mm )，使用超音波洗淨器 以純水淸洗6 0分鐘後以丙酮淸洗6 〇分鐘再風乾。之 後將不錄鋼試驗片放入5 0 °C、2 0 %的硝酸水中，靜置1 小時後取出試驗片以丙酮淸洗並風乾。上述殺菌劑以 海水（導電度1 0 0 m S / c m )稀釋1 〇 〇倍（殺菌劑濃度1 w t %) 當成試驗液（pH1.4)，放入l〇〇mL的聚容器內，將上述不 銹鋼試驗片1個1個地浸漬在其中。準備5個此聚容 器靜置在8(TC的恆溫室內。開始浸漬後的第6日取出 試驗片測定其重量。試驗片以純水淸洗5秒鐘後再以 -24- 1244466 五、發明説明（23) 丙酮淸洗5秒鐘，風乾後在矽膠乾燥的環境中使用可秤 量至0 · 0 1 m g的電子天秤測定其重量，以和實例4相同 的方法來計算減少重量。其結果如表6所示。 另外，鹽濃度6 · 9重量％的海水在3 〇 °c下靜置一晚，使 生菌數安定後以滅菌水稀釋成3 . 5重量％ (稱爲A 2 液）。海水（導電度1 0 m S / c m )中添加表6表示的殺菌劑 0.1重量％(?113.1)。在3〇t下靜置30分鐘（稱爲B2 液）。以和實例1 1相同的方法測定A2液、B2液的生 菌數。結果如表6所示。 另將上述的殺菌劑靜置在25 °C的恆溫室，在第19日 確認溶液狀態。其結果如表6所示。 (表中，聚丙烯酸簡寫爲PA、檸檬酸爲CA、蘋果酸爲 MA。） 從表6可知，和不添加保存穩定劑的實例14(實際上， 爲可使用的殺菌劑）比較，添加保存穩定劑的實例3不僅具 有防腐效果其保存安定性也高。另外，不添加防蝕劑的 比較例9,試驗片減少較多的重量。 表6 防蝕劑 保存穩 定齊 重量減少 (g/m2) 生菌殘存 率（％) 溶液狀態 實施例 1 3 P A C A，M A 0.19 0.12 沒有析出 實施例 14 PA Μ j\\\ 0.24 0.08 稍微混濁 比較例9 Μ 並 j \ \\ 1.08 0.16 沒有析出 [應用在產業上的可能性] -25- I244466 五、發明説明（24 ) 根據本發明，在使用膜分離裝置的水處理，可抑制裝 置配管的腐蝕且可有效地達到殺菌。因此，可增加殺菌 的頻率、降低pH値，可提高殺菌效果。 又，在本發明的水處理用殺菌劑中添加保存穩定劑時 可在維持殺菌效果及防蝕效果下提高保持安定性。 本發明特別適用於海水的淡化、鹹水的淡化等的工 程。 -26 - 1244466 五、發明說明（1) W [技術領域] 本發明係有關水處理用殺菌劑及以殺菌爲目的之水 處理方法。 [背景技術] 膜分離技術廣泛應用在海水及鹹水之淡化、醫療用 •工業用純水、超純水之製造、工業廢水之處理、食 品工業等領域。這些膜分離中因爲分離裝置受微生物 污染再加上穿透水的水質惡化，導致膜的滲透性或分離 性能降低。爲了避免發生這類重大問題，提議各種膜分 離裝置的殺菌法，一般採用將殺菌劑連續或間歇性地加 入饋入液的方法。最常使用的殺菌劑例如在價格、運 轉方面皆優良的氯系殺菌劑，其添加濃度爲 0. 1〜5 Oppm。另開發出一種添加便宜的硫酸，使膜分離 裝置的饋入液的pH値爲4以下，藉此可有效地進行殺 菌之方法（EP1031372A)。膜分離裝置的配管通常使用 不銹鋼等耐腐蝕性金屬，添加硫酸等而增加酸度後，因 爲金屬會進入Pourbaix diagram的腐鈾範圍，容易引起 配管的腐蝕。結果必須增加殺菌的頻率以提高殺菌的 效果，而發生增加殺菌的時間等問題。 在此考慮添加防蝕劑，但是一般具有防蝕作用的聚 胺、吡啶鐵鹽、聯銨等胺類防蝕劑爲陽離子性，會吸附 在陰電性的分離膜降低分離膜的性能。又，丁烷四羧酸 等酸類防蝕劑之防蝕效果較差。因此，以前的方法在維 持安定的膜性能時，不易同時提昇殺菌效果。 1244466 :·_____ 齡 l as:五、發明說明（2) [發明的揭示] 本發明的目的係克服上述以前技術的缺點，提供一種 具有高殺菌效果的水處理用殺菌劑及水處理方法。 爲了解決上述課題，本發明有下列幾點組成： (1) 一種水處理用殺菌劑，其特徵爲含有酸及防蝕劑， 且pH値爲4以下。 (2) —種水處理方法，其特徵係在使用分離膜的水處理 工程中，膜分離工程之前的任一項工程均添加含有 酸及防蝕劑且pH値爲4以下的水處理用殺菌劑。 (3) —種水處理裝置，其特徵係具有膜分離裝置，包含 在饋入此膜分離裝置的被處理液中添加含有酸及 防蝕劑的水溶液之方法。 [進行發明的最佳型態] 本發明的水處理係海水或鹹水的脫鹽、分離及淡 化、工業用純水或超純水的製造、工業廢水的處理、 食品工業的分離或濃縮、從廢水回收可利用的物質等 過程。 本發明的膜分離裝置係以造水、濃縮、分離等爲目 的，在加壓下將處理液饋入膜組件使分離或滲透液或濃 縮液之裝置。膜組件例如逆滲透膜組件、超過濾膜組 件、精密過濾膜組件等。膜分離裝置依主要使用膜組 件的種類可分爲逆滲透膜裝置、超過濾膜裝置、精密 過濾膜裝置等。 以本發明常用的逆滲透膜裝置爲例加以說明。通常 1244466 五、發明說明（8) 形成環氧琥珀酸鹽。其次，使環氧琥珀酸鹽在鹼性水溶 液中以氫氧化鈣爲觸媒，開環聚合後可得聚環氧琥珀酸 鹽。 馬來酸共聚物例如馬來酸和烯的共聚物、馬來酸和 甲基乙烯醚的共聚物等較適用。聚環氧琥珀酸、聚丙 烯酸、聚馬來酸或馬來酸共聚物的重量平均分子量依 水處理條件例如pH和溫度等會改變最適範圍，必須選 擇合於條件的分子量，通常在3 00〜1 00000的範圍，以 2000〜3 0000的範圍較理想。重量平均分子量在上述範 圍內其防蝕效果佳故較理想。理想的亞硝酸的鹼金屬 鹽以亞硝酸鈉常被使用。 在饋入水處理裝置的被處理液中添加酸及防蝕劑時， 可以個別添加亦可預先將兩者混合製作水處理用殺菌 劑再添加。預先製作水處理用殺菌劑後可以有效地進 行殺菌處理較理想。 本發明的水處理用殺菌劑中酸及防蝕劑的濃度分別 在5 Oppm (重量）〜50重量％的範圍較理想。酸及防蝕劑 的任一者或兩者的濃度超過50%後，殺菌劑的保存穩定 性容易變差。又，酸及防蝕劑的任一者或兩者的濃度低 於5 Oppm時，必須增加水處理用殺菌劑的添加量，殺菌 效果容易變差。 本發明的水處理用殺菌劑的pH値必須爲4以下，較 理想者爲1以下。pH値大於4時，爲了得到充分的殺 菌效果必須添加大量的殺菌劑較不理想。 -10- 1244466 五、發明說明（g) 用於本發明的水處理用殺菌劑的水以純水較適當。 使用的水若含有雜質，會發生與酸或防鈾劑反應產生析 出物、保存穩定性變差等現象。 酸和防蝕劑混合物的保存穩定性變差時，較理想的做 法是在水處理用殺菌劑中添加保存穩定劑。爲了避免 損壞水處理裝置的分離膜降低殺菌效果，較理想的保存 穩定劑係碳數8以下的羧酸及其鹼金屬鹽。較理想的 碳數8以下之羧酸例如至少一種選自乙酸、乳酸、琥 珀酸、酒石酸、檸檬酸及蘋果酸者。藉由添加這類的 保存穩定劑，酸和防蝕劑混合後經過長時間的保存仍可 維持其安定性。水處理用殺菌劑中的保存穩定劑之濃 度依殺菌劑中酸及防蝕劑的濃度而改變其最適範圍，通 吊較理想者係在50ppm(重量）〜50重量％的範圍。 殺菌劑在被處理液中的理想添加量依被處理液的鹽 濃度而變化，控制使被處理液的pH値小於4,且被處理 液中的防蝕劑的濃度在0.1 ppm〜1 %的範內較理想。若 被處理液的pH値大於4會降低殺菌效果。若防蝕劑 的濃度低於0. 1 ppm也會降低防蝕效果。相反地若防蝕 劑的濃度高於1 %時防蝕效果趨向飽和，不利於經濟面 的考量。 水處理用殺菌劑的理想添加量係被處理液的 1 〇 p p m (重量）〜1 0重量％的範圍內。殺菌劑的添量少於 1 Oppm時爲了提高殺菌效果必須增加殺菌劑中酸及防 蝕劑的濃度，可能導致水處理用殺菌劑的保存穩定性惡 -11- 1244466 五、發明說明（13) F-3導入氯的裝置。 A .貫通膜分離裝置的原水側出口部份的後處理裝置。 例如下列表示的裝置。 G- 1緩衝裝置。例如中和裝置 G-2放流裝置 B .其他。 亦可適當地設置處理廢水的裝置。 本發明的水處理裝置可在任意的場所設置泵。添加 酸及防蝕劑或這些的水溶液之設備以設置在A的取水 裝置、B的前處理裝置或前處理裝置前，及D的過濾器 前或過濾器後的任一個位置以上較理想。 爲了提高本發明的效果，水處理用殺菌劑、酸及防蝕 劑的添加裝置以能自動控制者較理想，最好具備能適當 地控制注入量的泵。測定饋入的被處理液及濃縮液的 pH防蝕劑的濃度等之設備設置在裝置內較理想。又， 爲了控制水處理用殺菌劑等的間歇添加，以具有能測定 時間裝置者較適當。以具有可自動運轉整體水處理裝 置的自動控制裝置較理想。 本發明的水處理裝置之構成零件例如配管、閥等，以 使用在PH4以下不易腐蝕者較埋想。使饋入的被處理 液的pH値爲4以下除了具有高殺菌效果之外，同時也 具有去除配管內水垢的效果。爲了預防氯等的氧化物 引起膜的劣化，可添加亞硫酸氫鈉，惟藉由使用本發明 的水處理用殺菌劑可明顯降低其添加量。 -15-COOX COOY A particularly desirable corrosion inhibitor is a compound selected from polyepoxysuccinic acid, ethylenediaminetetraacetic acid, polyacrylic acid and alkali metal salts thereof. Since these compounds contain atoms with large anions, such as oxygen and nitrogen, they have good adsorption properties on metal surfaces. Polyepoxysuccinic acid and its alkali metal salt were synthesized by the following method. In other words, using sodium tungstate as a catalyst, the maleate is epoxidized with hydrogen peroxide, -9-1244466. 5. Description of the invention (1G). In addition, when the amount of the water treatment fungicide added is more than 10% by weight, the load of the water treatment fungicide addition device is increased, and the energy consumption is increased, which is not conducive to economic considerations. For example, when pHO.5 is used as a water treatment bactericide with an inhibitor concentration of 0.1% by weight and the pH of the liquid to be treated is 2.5, approximately 1% by weight of the water treatment bactericide is added. In the water treatment method of the present invention, an acid and an anticorrosive agent may be separately added to the liquid to be treated. The amount of acid added to the liquid to be treated is considered from the viewpoint of sterilization effect, and more than 10 p p m (weight) is appropriate. From the viewpoint of economic aspects and prevention of corrosion of piping and other equipment, less than 1% by weight is ideal. When sulfuric acid is used, the amount added is proportional to the salt concentration of the liquid to be treated. For example, by adding 50 ppm sulfuric acid to physiological saline (table salt concentration 0.9% by weight) that has been subjected to pressure sterilization (120 ° C, 15 minutes), the pH can be reduced to 3.2, but the pressure sterilization (1 2 (TC, 1 5 3 minutes of seawater and commercially available artificial seawater (with a salt concentration of about 3.5% by weight) when used as the liquid to be treated, even if 100 ppm of sulfuric acid to be treated is added, the P 値 値 is between 5.0 and 5.8. This is mainly affected by the M alkalinity of the seawater. In order to reduce the pH of the seawater to below 4, it is usually desirable to add sulfuric acid above 120 ppm (weight). From an economic point of view and to prevent corrosion of piping temple equipment From the viewpoint of starvation, the upper limit of the amount of sulfuric acid added is preferably 400 ppm or less, and more preferably 300 ppm or less. When the sulfuric acid concentration in the above seawater and artificial seawater is 150ppm and 200ppm, the mouth 11 値 is卩 113.2 ~ 3.6, 卩 112.8 ~ 2.9. That is, as the sulfuric acid addition concentration increases, the pΗ irregularity of the treatment liquid will decrease. -12- 1244466 V. Description of the invention (11) Anticorrosive agent concentration in the treatment liquid The optimum range depends on the type of liquid being treated and The processing conditions vary, but it is usually in the range of 0.1 Ρ Π Π1 (weight) to 1% by weight. From the economic aspect and the simplicity of water treatment operations, it is more appropriate to be in the range of 1 to 500 ppm. For example, when wastewater with ρ 0 1.0 and a salt concentration of about 8% is subjected to water treatment at 3 5 t, the range of the corrosion inhibitor in the treated liquid is preferably 1 to 100 PP m. The acid and the The liniment is not limited in the position to be added, as long as it is added before the liquid to be processed is fed into the membrane separation device:] ::. It is ideal to add the previous step for the sterilization membrane separation device of the membrane separation device. Water treatment At the same time, it is ideal to perform sterilization treatment, and it can also be stopped. (% Into sterilization treatment. It is ideal to intermittently add acid and mothproofing agent. It is better to add each time within the range of about 0.5 to 2.5 hours. The frequency is more suitable once a day to once a month. The addition time and the addition frequency are ideally changed according to changes in the amount of water penetrating the membrane, changes in the number of bacteria and organic carbon in the concentrated solution, and increase in the membrane pressure. As for the sterilization of the membrane, it can be used in water treatment equipment At the end, the film is immersed in an aqueous solution containing an acid and an anticorrosive agent. When the acid and the anticorrosive agent are added separately, the individual addition frequency can also be changed. For example, the acid is added every other day for 0.5 to 2.5 hours. And the anticorrosive agent is added for 1 week 1 time and acid phase_time. Especially when the anticorrosive agent is expensive and its anticorrosive effect is sufficient, from the economic point of view, in order to reduce the frequency of adding the anticorrosive agent, only add the acid and simultaneously add the acid and the anticorrosive agent. Appropriate. The water treatment device having the membrane separation device of the present invention is, for example, a device composed of A to Η listed below in the description of the invention (12) 5. A · Water intake device. The device for collecting the liquid (raw water) in the device is usually composed of a water pump, a medicine introduction device, and the like. B. Pre-treatment device penetrating the water intake device. A device that feeds the liquid to be treated into the separation membrane device to a pretreatment to remove suspended matter, emulsion, etc. in the liquid to be treated, and feeds a part of the medicine. For example, it can be composed in the following order. B-1 Condensation filtration, device B-2 Ion exchange filtration device Ultrafiltration device and precision filtration device can also be used instead of B-1 and B-2. B-3 Equipment for feeding medicaments such as coagulants, bactericides, ρ η regulators. C. The equipment passes through the middle tank of the pretreatment device as required. It has the functions of water volume adjustment and water quality buffering. D. A filter that passes through the intermediate tank when C is installed, or that passes through the pretreatment device when c is not provided. The solid impurities of the liquid to be processed fed into the membrane separation device are removed. Ε · Membrane separation device. It consists of a high-pressure pump and a separation membrane module. Set up a number of membrane separation devices, these can be set side by side or straight. When it is arranged in a straight row, a pump can be installed between the membrane separation devices. This pump can increase the water pressure when the separation membrane device in the subsequent stage feeds the liquid to be treated. F. Post-treatment device for the permeate outlet portion of the separation device penetrating the membrane. For example, the device shown below. F-1 degassing device. With decarbonation function. F-2 calcium tower. -14- 1244466 V. Description of the invention (14) The water treatment method of the present invention is suitable for water treatment using a membrane separation device. It is especially suitable for water refining processes such as desalination of seawater, desalination of salt water, manufacture of industrial water, manufacture of ultrapure water and pure water, manufacture of pure water for medicine, tap water turbidity removal, and high treatment of tap water. In addition, in terms of food concentration, etc., when an organic substance that is easily dissociated by a conventional oxidizing bactericide is separated or concentrated, the organic substance can be concentrated or recovered without dissociation, and the effect of the present invention is remarkable. It can prevent the occurrence of trihalomethane caused by chlorine sterilization during the production of concrete. The water treatment method of the present invention is particularly effective in the sterilization treatment of bacteria produced from seawater. Chlorine fungicides are usually effective for sterilization. When the water treatment device has a membrane separation device, for example, in any of the above-mentioned devices A to D, a continuous or intermittent injection of a chlorine fungicide is performed. According to this method, as long as the to-be-treated liquid is fed, as long as no resistant bacteria appear, it can be completely sterilized. In order to prevent deterioration of the reverse osmosis membrane by the chlorine bactericide, a reducing agent typified by sodium bisulfite is usually added in the previous step of the membrane separation device. However, microorganisms tend to multiply in the treated liquid after reducing and removing chlorine due to the reducing agent. In addition, unlike the raw seawater before adding the fungicide, there are various micro-organisms, but a specially selected microbiome exists, which may contain most acid-resistant bacteria. Intermittently adding chlorine bactericide in the pretreatment process and injecting a reducing agent in the previous step of the membrane separation unit can solve this problem. This method is also effective for preventing degradation of the film. The interval between the injection of the chlorine fungicide, for example, is based on the quality of the seawater raw water, that is, the living conditions of the microorganisms, and it is preferably performed once a day to 6 months and once every 30 minutes to 2 hours. In accordance with the timing of the addition of this chlorine bactericide, and taking into account the -16- 1244466 of chlorine-containing bactericide water V. Description of the invention (15) Move, feed the reducing agent between the pretreatment device and the membrane separation device to inactivate the bactericide More appropriate. In addition, it is desirable to add the sterilizing agent and acid for water treatment of the present invention to the aqueous solution fed into the membrane separately at this time to sterilize the membrane separation device. In this way, compared with the method of continuously injecting the bactericidal agent in the pretreatment process by intermittently injecting the chlorine bactericidal agent, it has a significant effect in reducing the cost of medicines and the like. The treatment method can achieve such an effect for the first time. The previous sterilization method could not be achieved because of the poor sterilization effect. Examples The present invention is specifically described in synthesis examples and examples, but these examples of the present invention are limited. First, the medicinal solution and the like used in the examples will be described. < Synthesis example of polyepoxysuccinate > According to synthesis of payne (J. Org. Chem., 24, 54 (1959)), a polyepoxysuccinate was synthesized by the following procedure. In a 2 L three-necked flask, 280 g of maleic anhydride and ultra-pure 4 2 8 m 1 were placed to dissolve. With cooling and maintaining at room temperature, 500 g of a 100% by weight potassium hydroxide aqueous solution was dropped into the above water through a dropping funnel. Next, 18 g of sodium tungstate was added, and 3 2 g of 35 wt% peroxy water was added dropwise. After stirring for 30 minutes, 1 15 g of 48% by weight aqueous potassium hydrogen solution was slowly added. At this time, the flask was rapidly cooled to maintain the reaction temperature at 55 to 65 ° C. The next 30 minutes remained at 65 to 60. (: An aqueous solution of potassium cyclamate was prepared. After cooling to room temperature, this aqueous solution was concentrated to form a chlorinated solution to obtain anti-drug and treatment agents or fruits. In Oxo-17-1244466 V. Description of the invention (16) 3 0 0 m 1 and injected with 1 L of lactone, Shen Dianwu, which produced 7 l · :, isolated potassium epoxysuccinate alone. Next in 2 0 0 m 1 In a round-bottomed flask, put 1 0.4 g of potassium epoxysuccinate and 50 g of ultrapure water, add 48% by weight potassium hydroxide, and adjust the pH of the aqueous solution to 10.3. Then add potassium argon oxide 0.41 g was reacted at 80 ° C for 6 hours. Then, the insoluble matter was filtered after cooling to room temperature, and water was removed at a bath temperature of 40 ° C using a rotary evaporator to obtain a white solid. The molecular weight of the obtained polyepoxysuccinate was measured by gel permeation chromatography (GPC). Specifically, a test product of 200 PPm was prepared. Polyethylene glycol with a known molecular weight was used as a standard substance. Take out the calibration curve and calculate the molecular weight of the test product. The molecular weight and weight average molecular weight of the obtained polyepoxysuccinate Mw = 20900 (n = 100, Ww / Mn = 1.00). Examples 1 to 3 20% by weight of sulfuric acid was added to pure water (conductivity 10V s / cm) and 0.1 wt% of the corrosion inhibitor shown in Table 1. , To prepare a fungicide for water treatment (pHO. 6). SUS 3 1 6 L stainless steel test piece (2 0 X 3 0 丨 uni X 1 nil 丨 丨) whose surface has been hoared with a file No. 3 2 0, Let the 丨 | ”ultrasonic cleaner be washed with pure water for 60 minutes, and then air-dried with W_ 淸 冼 60 minutes. Dilute the above water treatment with seawater (conductivity 100 m S / cm) 100 times. Using a biocide (biocide concentration of 1% by weight), a test solution (ρ Η 1.2) with a total amount of 1000 ni L was placed in a 100 m L polycontainer, and the stainless steel test piece was placed. One by one immersed in it. Prepare 10 of these polycontainers to stand in a greenhouse at 80 ° C. Take out the test plant Γ on the 4th | and 7th days after the start of the dipping and measure the weight. Pure water should be washed with C after 5 seconds -18-1244466 V. Description of the invention (17) For 5 seconds, after air-drying, use an electron that can be leveled to 0.001 mg in a silicone-dry environment. Measure the weight on the floor, find 5 The average roots of roots are evaluated as follows: The weight reduction (a) from the start of immersion to the fourth day and the weight reduction (b) from the 4th to the 7th are based on the following (A) (g / m2) = (weight of test piece before immersion-weight of test piece on the 4th day) / surface weight reduction of test piece (b) (g / m2) = (4th The weight of the test piece on the day-the weight of the test piece on the 7th) / the surface area of the test piece. Next, the above-mentioned weight reductions (a) and (b) are individually calculated according to the following methods. Weight reduction ratio. Weight reduction (a) ratio = weight reduction with uranium inhibitor (a) / weight reduction without corrosion inhibitor (a) weight reduction (b) ratio = weight reduction with corrosion inhibitor (b) / corrosion inhibitor-free Weight reduction (b) The average weight ratio of the weight reduction U) ratio and the (b) ratio was taken as the weight reduction rate. The results are shown in Table 1. (In the table, the polyepoxysuccinate potassium salt is abbreviated as PES, ethylenediaminetetraacetic acid tetrasodium is abbreviated as EDTA, and polyacrylic acid is abbreviated as pa.) Comparative Example 1 was performed in the same manner as Example 1 except that no anticorrosive agent was added. experiment of. The results are shown in Table 1. Comparing this comparative example without the addition of an anticorrosive agent to Examples 1 to 3, a large weight reduction rate indicates that the test piece will corrode. -19- 1244466 V. Description of the invention (18) Table 1 Weight reduction rate of corrosion inhibitors-Example 1 PES 0.37 Example 2 EDT A 0.58 Example 3 PA 0.67 Comparative Example 1 钲 j \\\ 1.00 Example 4 ~ 6 Adding The test solution was prepared by adding 10 ppm of the corrosion inhibitor shown in Table 2 to seawater (conductivity: 100 mS / cm) with sulfuric acid and a pH of 1. A sus 3 04 stainless steel test piece (20 x 30 mm x 1 leg) with a surface honing of a file No. 3 and 20, was washed with pure water for 60 minutes using an ultrasonic cleaner, and then washed with acetone for 60 minutes. Air dry. The test solution 100 m 1 was placed in a 100 ml polycontainer, and the stainless steel test pieces were immersed one by one. Prepare 5 polycondensation containers in a thermostatic chamber at 35 ° C for 3 days, and heat up to 80 ° C, then continue to stand for 17 hours. The test piece was taken out, washed with pure water for 30 seconds, and then washed with acetone for 10 seconds. The weight loss due to rot was measured according to the following method. The average weight of 5 test pieces was used as the reduced weight. Weight reduction (g / m2) = (weight of test piece before immersion-weight of test piece after 3 days of immersion) / surface area of test piece The results are shown in Table 2. (In the table, the polyepoxysuccinate potassium salt is abbreviated as PES, ethylenediamine tetraacetic acid tetrasodium is abbreviated as EDTA, and butanetetracarboxylic acid is abbreviated as bTC.) Comparative Examples 2 and 3 Except that the corrosion resistance shown in Table 2 was changed Except for the agent, the same experiment as in Example -20-1244466 was performed. V. Experiment of the invention description (19). From Table 2, it can be seen that under acidic conditions with p Η 値 of 1, examples of corrosion inhibitors such as Timury PES, EDTA, and polyacrylic acid, and comparative example 2 without the antioxidants of Timury 2, and butane with organic carboxylic acid added Comparative Example 3 of the tetracarboxylic acid was compared, and as a result, it had a better anticorrosive effect. Table 2 Corrosion inhibitor concentration (ppm) Weight reduction (g / m2) Example 4 PES 10 0.19 Example 5 EDT A 10 0.14 Example 6 PA 10 0.3 8 Comparative example 2 M-27.9 Comparative example 3 BTC 10 17.9 Example 7, 8 To seawater (conductivity 9 8 m S / cm) to which sulfuric acid was added and the pH was adjusted to 2.5, an anti-contact agent 10 ppm shown in Table 3 was added to prepare a test solution. Su S 3 0 4 stainless steel test piece (15 mm X 2 0 mm X 1 mm) whose surface has been honed with a file No. 240, and then washed with pure water for 30 minutes using an ultrasonic cleaner Rinse with acetone for 30 minutes and air-dry. The test solution 1000 m 1 was put in 100 m L of Juguyi, and the stainless steel test pieces were immersed one by one. Five such polycontainers were prepared and left in a constant temperature room at 35 ° C for 8 days. The test piece was taken out, washed with pure water for 30 seconds, and then washed with acetone for 10 seconds. The weight reduction due to corrosion was measured in the same manner as in Example 4. The results are shown in Table 3. (Sodium nitrite in the table is abbreviated as NaN02) Comparative Example 4 -21-1244466 V. Description of the invention (20) The same experiment as in Example 7 was performed except that no corrosion inhibitor was added. The results are shown in Table 3. In this example without the use of an anti-stabbing agent, the test piece was reduced in weight. Table 3 ·· Corrosion inhibitor concentration (ppm) Weight reduction (g / m2) Example 7 NaN02 10 14.2 Example 8 EDT A 10 9.8 Comparative Example 4 and > \ N \-23.5 Example 9, 1 0 When sulfuric acid was added and The test solution was prepared by adding 10 ppm of the anti-corrosive agent shown in Table 4 to seawater (conductivity 100 m S / cm) with a pH of 1. SUS 3 0 4 and SUS 3 1 6 stainless steel test pieces (20 mm X 3 0 awake) X 1 min after the surface was hoared with a file No. 3 2 0, washed with pure water using an ultrasonic cleaner After 60 minutes, wash with acetone for 60 minutes and air-dry. 100 ml of the test solution was placed in a 100 mL polycontainer, and the stainless steel test pieces were immersed one by one. Prepare 10 of these polycontainers and let stand 4 |: 1 in a constant temperature room at 80 ° C. Take out the test piece and rinse it with pure water for 5 seconds and then rinse with acetone for 5 seconds. The heavy scene due to the reduction in corrosion was measured by the method of phase 4 of Example 4. The results are shown in Table 4. (In the table, the polyepoxy potassium succinate is abbreviated as PES, and the sodium salt of the maleic olefin copolymer is abbreviated as P M 0.) Comparative Example 5 The same experiment as in Example 9 was performed except that Γ was not added with an anticorrosive agent. . The results are shown in Table 4. In the case of wood without anti-corrosive agent, the test piece has reduced weight compared to -22-1244466 V. Invention Description (21). Table 4 Uranium protection agent (Chen) (ppm) Weight reduction (g / m2) SUS304 SUS316 Example 9 Example 1 〇PES 10 0.0833 7.71 PMO 10 36.1 8.35 Comparative Example 5-43.7 23.7 Example 1 1, 1 2, Reference Example 1 Seawater with a salt concentration of 5.8% by weight was left to stand overnight at 30 ° C, and the bacterial count was stabilized and diluted with sterilized water to 3.5% by weight (referred to as A solution). The pH of solution A is 6.6. To the seawater (conductivity 98.5mS / cm) to which 1% by weight of the corrosion inhibitor of Table 5 has been added, 1% by weight of the above-mentioned A liquid is added, and sulfuric acid is added to make the pH 3.0, and it is left to stand at 3 (TC for 30 minutes (referred to as Solution B). Measure the number of bacteria in Solution B. The number of bacteria is measured using 1 / 20RI medium (medium for measuring marine bacteria), and the communities that appear after culturing at 30 ° C for 6 days are counted as bacteria. The number surviving rate represents the number of viable bacteria relative to the time when pΗ is not adjusted (Liquid A), that is, the remaining number of viable counts (%) is calculated by the following formula. The remaining number of viable counts (% H after reaction (B The number of germs in liquid) / (the number of germs in the case of no pH adjustment (Liquid A)) X 1 〇 The results are shown in Table 5. From Table 5, it can be seen that even with the addition of PES and EDTA, the sterilization effect of sulfuric acid is poor. It can still maintain excellent bactericidal effect. Among the reference examples, no anti-corrosive agent is added, although its bactericidal effect is good but it does not have anti-corrosive effect. Comparative Examples 6 ~ 8 -23-1244466 V. Description of the invention (22) In addition to changing B The same experiment as in Example 11 was performed except that p Η 値 was 7.2 or 6 · 6. The results are shown in Table 5. The ρ Η 値 of the β solution was higher These comparative examples are shown in Table 5. There is no bactericidal effect. 0 Corrosion inhibitor PH Residual bacteria (%) Example 1 1 PES 3.0 0.07 ~ Example 1 2 EDT A 3.0 0.5 ~~ ^ Reference example 1 None 3.0 0.05 Comparative example 6 PES 7.2 39.5 Comparative Example 7 EDTA 7.2 24.1 ~ Comparative Example 8 None 6.6 ---- 39.6 Example 1 3, 1 4, Comparative Example 9----- 1 Add sulfuric acid to pure water (conductivity 1 0 // S / cm) 20wt%, Table 6 anti-corrosive agent 0 · 1 wt% prepared bactericidal agent for water treatment device. For example 1 3, sodium citrate and malic acid, each containing a stabilizing agent, were added at a weight of 0.0% by weight. Su S 3 0 4 stainless steel test piece (2 〇111111 x 3 〇cm X 1 mm) whose surface has been honed with a file No. 3 2 0. Rinse with pure water for 60 minutes using an ultrasonic cleaner. Rinse with acetone for 60 minutes and air-dry. After that, put the non-recorded steel test piece in 50 ° C, 20% nitric acid water, and leave it for 1 hour. Take out the test piece and rinse with acetone and air-dry. (Conductivity: 100 m S / cm) diluted 1000 times (fungicide concentration 1 wt%) as a test solution (pH 1.4), put in a 100 mL polycontainer, The above stainless steel test pieces were immersed one by one. Five of these polycontainers were prepared and left to stand in a thermostatic chamber at 8 ° C. The test pieces were taken out on the sixth day after the start of immersion to measure their weight. The test pieces were rinsed with pure water After 5 seconds, use -24-1244466. 5. Description of the invention (23) Rinse with acetone for 5 seconds. After air-drying, use an electronic balance that can be weighed to 0 · 0 1 mg to measure its weight in a silicone-dry environment. Example 4 uses the same method to calculate the weight reduction. The results are shown in Table 6. In addition, seawater with a salt concentration of 6.9% by weight was allowed to stand overnight at 30 ° C, and the bacterial count was stabilized, and then diluted with sterilized water to 3.5% by weight (referred to as A 2 solution). In seawater (conductivity 10 m S / cm), 0.1% by weight (? 113.1) of the bactericide shown in Table 6 was added. Let stand for 30 minutes at 30t (referred to as B2 solution). The bacterial counts of A2 liquid and B2 liquid were measured in the same manner as in Example 11. The results are shown in Table 6. In addition, the above-mentioned bactericide was left to stand in a constant temperature room at 25 ° C, and the solution state was confirmed on the 19th day. The results are shown in Table 6. (In the table, polyacrylic acid is abbreviated as PA, citric acid is CA, and malic acid is MA.) As can be seen from Table 6, compared with Example 14 (in fact, a usable fungicide) without the addition of a storage stabilizer, storage was added. Example 3 of the stabilizer not only has an antiseptic effect, but also has high storage stability. In addition, in Comparative Example 9 in which no corrosion inhibitor was added, the test piece was reduced in weight. Table 6 Preservative stability and weight reduction (g / m2) Residual bacterial percentage (%) Solution state Example 1 3 PACA, MA 0.19 0.12 No precipitation Example 14 PA Μ j \\\ 0.24 0.08 Slightly turbid Comparative Example 9 Μ and j \ \\ 1.08 0.16 No precipitation [Possibility of application in industry] -25- I244466 V. Description of the invention (24) According to the present invention, in the water treatment using a membrane separation device, the corrosion of the piping of the device can be suppressed and Can effectively achieve sterilization. Therefore, the frequency of sterilization can be increased, the pH can be lowered, and the sterilization effect can be improved. In addition, when a storage stabilizer is added to the bactericidal agent for water treatment of the present invention, the stability can be improved while maintaining the bactericidal effect and the anticorrosive effect. The present invention is particularly suitable for processes such as desalination of seawater and desalination of salt water. -26-1244466 V. Description of the invention (1) W [Technical field] The present invention relates to a water treatment bactericide and a water treatment method for the purpose of sterilization. [Background technology] Membrane separation technology is widely used in the desalination of seawater and salt water, medical use • Industrial pure water, manufacture of ultrapure water, treatment of industrial wastewater, food industry and other fields. In these membrane separations, because the separation device is contaminated with microorganisms and the water quality of the penetrating water is deteriorated, the membrane permeability or separation performance is reduced. In order to avoid such a major problem, sterilization methods of various membrane separation devices are proposed, and a method of continuously or intermittently adding a bactericide to the feed solution is generally used. 1〜5 Oppm。 The most commonly used fungicides are, for example, chlorine-based fungicides that are excellent in terms of price and operation, and whose added concentration is 0.1 to 5 Oppm. Another method has been developed to add cheap sulfuric acid to make the feed liquid of the membrane separation device pH 4 or lower, thereby enabling effective sterilization (EP1031372A). Corrosion-resistant metals such as stainless steel are usually used for the piping of the membrane separation device. When sulfuric acid is added to increase the acidity, the metal may enter the uranium-corrosive range of the Pourbaix diagram, which may cause corrosion of the piping. As a result, the frequency of sterilization must be increased to increase the effect of sterilization, and problems such as an increase in the time of sterilization occur. It is considered to add an anticorrosive agent here, but generally amine anticorrosive agents, such as polyamines, iron pyridine salts, and diammonium, which have an anticorrosive effect, are cationic and adsorb on the anion separation membrane to reduce the performance of the separation membrane. In addition, acid corrosion inhibitors such as butanetetracarboxylic acid have a poor corrosion resistance. Therefore, in the previous method, it is not easy to improve the sterilization effect while maintaining stable film performance. 1244466: · _____ Age l as: V. Description of the invention (2) [Disclosure of the invention] The purpose of the present invention is to overcome the shortcomings of the foregoing prior art, and provide a bactericide for water treatment and a water treatment method with high sterilization effect. In order to solve the above problems, the present invention has the following components: (1) A bactericide for water treatment, which is characterized by containing an acid and an anticorrosive agent, and has a pH of 4 or less. (2) A water treatment method, characterized in that in a water treatment process using a separation membrane, any process before the membrane separation process is added with a water treatment fungicide containing an acid and an anticorrosive agent and having a pH of 4 or less . (3) A water treatment device characterized by having a membrane separation device comprising a method of adding an aqueous solution containing an acid and an anticorrosive agent to a liquid to be treated fed to the membrane separation device. [The best form of invention] The water treatment system of the present invention is desalination, separation and desalination of seawater or salt water, production of industrial pure or ultrapure water, treatment of industrial wastewater, separation or concentration of food industry, and removal of wastewater Processes such as recycling available materials. The membrane separation device of the present invention is a device for generating water, concentrating, separating, etc., and feeding the treatment liquid to the membrane module under pressure to separate or permeate the liquid or concentrate the liquid. The membrane module is, for example, a reverse osmosis membrane module, an ultrafiltration membrane module, a precision filtration membrane module, and the like. Membrane separation equipment can be divided into reverse osmosis membrane equipment, ultrafiltration membrane equipment, precision filtration membrane equipment, etc. according to the types of membrane components mainly used. The conventional reverse osmosis membrane device of the present invention will be described as an example. Usually 1244466 V. Description of the invention (8) The formation of epoxy succinate. Secondly, the epoxy succinate is made of calcium hydroxide as a catalyst in an alkaline aqueous solution, and a polyepoxysuccinate can be obtained after ring-opening polymerization. Copolymers of maleic acid such as a copolymer of maleic acid and olefin, a copolymer of maleic acid and methyl vinyl ether, and the like are suitable. The weight average molecular weight of polyepoxysuccinic acid, polyacrylic acid, polymaleic acid or maleic acid copolymer will change the optimal range depending on water treatment conditions such as pH and temperature, etc. It is necessary to choose a molecular weight suitable for the conditions, usually between 3 00 ~ A range of 1 00000, and a range of 2,000 to 30,000 is preferable. A weight average molecular weight within the above range is preferable because it has a good anticorrosive effect. The ideal alkali metal salt of nitrous acid is often used as sodium nitrite. When the acid and the corrosion inhibitor are added to the liquid to be fed into the water treatment device, they may be added individually or they may be mixed in advance to prepare a water treatment bactericide and then added. It is preferable to prepare a bactericide for water treatment in advance so that it can be effectively sterilized. The concentrations of the acid and the corrosion inhibitor in the bactericide for water treatment of the present invention are preferably in a range of 5 Oppm to 50% by weight, respectively. When the concentration of either or both of the acid and the corrosion inhibitor exceeds 50%, the storage stability of the fungicide is liable to deteriorate. When the concentration of either or both of the acid and the corrosion inhibitor is less than 5 Oppm, it is necessary to increase the amount of the sterilant for water treatment, and the sterilization effect is liable to deteriorate. The pH of the water treatment fungicide of the present invention must be 4 or less, and more preferably 1 or less. When the pH is greater than 4, it is not desirable to add a large amount of bactericide in order to obtain a sufficient bactericidal effect. -10- 1244466 V. Description of the invention (g) Pure water is more suitable as the water used as the bactericide for water treatment of the present invention. If the water used contains impurities, it may react with acids or uranium inhibitors to produce precipitates and deteriorate storage stability. When the storage stability of the acid and corrosion inhibitor mixture is deteriorated, it is more desirable to add a storage stabilizer to a water treatment fungicide. In order to avoid damaging the separation membrane of the water treatment device and reduce the sterilization effect, the ideal storage stabilizer is a carboxylic acid having an carbon number of 8 or less and an alkali metal salt thereof. Preferred carboxylic acids having a carbon number of 8 or less are, for example, at least one selected from the group consisting of acetic acid, lactic acid, succinic acid, tartaric acid, citric acid, and malic acid. By adding such a storage stabilizer, the stability of the acid and the corrosion inhibitor can be maintained even after long-term storage. The concentration of the storage stabilizer in the water treatment fungicide varies depending on the concentration of the acid and the corrosion inhibitor in the fungicide. The optimum range is 50 ppm (by weight) to 50% by weight. The ideal amount of bactericide in the treated liquid varies depending on the salt concentration of the treated liquid. Control the pH of the treated liquid to be less than 4, and the concentration of the anticorrosive in the treated liquid is in the range of 0.1 ppm to 1%. Inside is ideal. If the pH of the liquid to be treated is greater than 4, the sterilization effect is reduced. If the concentration of the anticorrosive agent is less than 0.1 ppm, the anticorrosive effect will be reduced. Conversely, if the concentration of the anticorrosive is higher than 1%, the anticorrosive effect tends to be saturated, which is not conducive to economic considerations. The ideal addition amount of the bactericide for water treatment is in the range of 10 p p m (weight) to 10% by weight of the liquid to be treated. When the amount of bactericide is less than 1 Oppm, in order to improve the bactericidal effect, the concentration of the acid and the corrosion inhibitor in the bactericide must be increased, which may cause the storage stability of the bactericide for water treatment. -3 Device for introducing chlorine. A. Post-treatment device that passes through the raw water side outlet portion of the membrane separation device. For example, the device shown below. G-1 cushioning device. For example, neutralization device G-2 discharge device B. Other. A device for treating waste water may be provided as appropriate. The water treatment device of the present invention can be provided with a pump at any place. The equipment for adding an acid and an anticorrosive agent or an aqueous solution of these is preferably placed above the water intake device of A, the pre-treatment device or pre-treatment device of B, and the filter D before or after the filter. In order to improve the effect of the present invention, it is desirable that the device for adding a bactericide, an acid and an anti-corrosive agent for water treatment can be automatically controlled, and it is preferable to include a pump capable of appropriately controlling the injection amount. It is desirable that the equipment for measuring the concentration of the pH inhibitor and the like of the fed liquid and the concentrated liquid be installed in the device. In addition, in order to control the intermittent addition of a bactericide for water treatment, it is more appropriate to have a device capable of measuring time. It is preferable to use an automatic control device that can automatically operate the overall water treatment device. The components of the water treatment apparatus of the present invention, such as piping and valves, are more likely to be used if they are less likely to corrode at pH 4 or lower. Adjusting the pH of the feed solution to be 4 or lower has a high sterilization effect and also has the effect of removing scale in the pipes. In order to prevent deterioration of the membrane caused by oxides such as chlorine, sodium bisulfite may be added. However, by using the fungicide for water treatment of the present invention, the amount of addition can be significantly reduced. -15-