TW201036921A

TW201036921A - Activated metal salt flocculant and process for producing same

Info

Publication number: TW201036921A
Application number: TW099105476A
Authority: TW
Inventors: Toshikatsu Miki; Takuya Murata; Jun Fukaishi
Original assignee: Univ Yamaguchi; Yamaguchi Tech Licensing; Aproads Co Ltd
Priority date: 2009-02-25
Filing date: 2010-02-25
Publication date: 2010-10-16
Also published as: WO2010098492A1; JP5498477B2; CN101970072A; TWI402220B; KR20100120279A; JPWO2010098492A1

Abstract

Disclosed is an activated metal salt flocculant in which the flocculation activity of a metal salt flocculant is significantly improved. The activated metal salt flocculant is produced by electrolyzing a metal salt flocculant or an aqueous solution containing the metal salt flocculant.

Description

201036921 六、發明說明：【發明所屬之技術領域】本發明係關於用於淨化潔淨水、廢水、產業用廢水、農 .業用廢水等之污水之凝集劑。尤其是關於對包含水溶性或勝體狀有機物之污水，具有顯著效果之活性凝集劑及其製造方法。【先前技術】 ❹ 在含序游性污濁體或水溶性去除對象物質之農業用廢水、產業用廢水或家庭用廢水之廢水之淨化，或用於形成飲用水之水源水（在本說明書中將該等統稱為污水）之淨化中，係單獨或併用：利用過濾分離處理、吸附分離處理、凝集沉殿處理、凝集上浮處理、電化學處理等所謂之物理化:手^而除去懸浮物或溶解雜質，以及利用好氣性菌或厭现性囷之生物代謝而分解去除對象物質之生物學手段。在物理化學手段中，作為溶解或㈣等而存在之去除對象物質:通常係使用凝集劑，使其成為粗粒或絮狀令其沉殿或懸浮而予分離去除。作為凝集劑通常為紹系、鐵系、鎮系等之金屬鹽，尤其是包含該等金屬之聚合物具有較高之效果。、 J 凝集劑之作用，因通常污水中之濁質膠體於有負電荷’故上述金屬鹽凝集劑係藉由在水中例如鋁羥基錯合物等成為正電中幻粒子集合呈絮狀，戈是將二於而中和電荷，並使膠體質、或腐黑物類等之有機物予以之專角錢蛋白于以皿析之作用，使去除對象 I46278.doc 201036921 物成為絮片等塊狀化者。先前，作為一般使用之金屬鹽系凝集劑，主要係使用硫酸銘（硫酸礬土： Al2(s〇4)3)或聚氣化鋁（PAC : [Al2(OH)nCl6_n]m) (n=l〜5、msi〇)等之鋁系、硫酸亞鐵（綠礬：FeS04_7H20) 或氣化鐵（FeCl3.6H20)或以羥基置換硫酸鐵之硫酸基之一部份而成之聚硫酸鐵（[Fe2(OH)n8(S04)33_n/2]m)等之鐵系、還有鐵-二氧化矽無機高分子之聚合矽酸鐵（PSI : [(Si02；). (Fe2〇3)i 〜3]η)(η=50 〜200)等。此外還有併用該等之凝集劑，或單獨使用陽離子系、陰離子系或非離子系之高分子凝集劑（凝集助劑）之情況。作為該等之有機凝集劑，有陽離子系之例如苯胺衍生物、聚伸乙亞胺等之胺類、聚酿胺、聚丙稀酿胺等之酿胺系凝集劑，主要用於去除廢水或糞尿等、或綠藻、綠藻類、細菌等之藻類。X ’有機凝集劑中之陰離子系者例如有聚丙稀Ί，特別用於使被處理水之PH從t性至驗性之情況通吊較多用於含有重金屬氫氧化物等陽離子荷電粒子 ^廢液{列如紙漿工廠廢水、金屬機械工廠廢水水、電鍍廢水等之情況。、忙尾又非雜子系例如有聚環負r笼；+、·《· 性〜酸性之情況，在氧乙广等’尤其適用於PH中 ψ Λ, 粘土知取廢水、選礦廢水等 …機貝W物之沉降促進、過滤金屬鹽凝集劑使用。 ^况其係合併又，還揭示有利用電性分解）之凝集去除隹本忒明書中稱為 τ水中之有機物之方法。作為利用電解 146278.doc 201036921 污水之處理手段，-般係使用金屬電極，在電解時藉由該電極之溶出而將陽離子供給至被處理水中者，例如專利文獻1 ' 2中係使用鋁或鐵作為電極。又，藉由pAc使縣浮粒 • +凝集後’藉由電解所造成之氣泡之產生使凝集粒^出水、®，而形成浮泡者（專利文獻3)，χ，關於含有難分解性有機物之廢水，首先，藉由好氣性菌分解後，添加含有金屬離子之凝集劑、例如PAC或氣化鐵進行電解氧化還原，藉 ❹此促進該金屬離子與難分解性有機物之錯合物之生成: (專利文獻4)，或是對含有二氧化石夕之廢水，藉由將鐵作為電極之電解操作，使一邱松白人_於 ^ 便。卩伤包含一乳化矽-鐵之凝集劑在系内形成’從而除去被去除物質者（專利文獻5)等。但，由於該等之利用電解之污水之處理均為對包含於污水中之污濁物質本身發揮作用者，故存在必須採用大型化之裝置、或在實地進行電解之問題。再者在污水處理中，結合上述利用金屬鹽凝集劑之浮 ❹游物之去除處理，亦有進行稱為所謂活性污泥法之利用細 i之有機物之分解處理。例如在農業用廢水之處理等時，亦常合併進行好氣性菌處理與厭氣性菌處理。 •、如域述’在污水處理時，通常首先必須將凝集劑所造成之子游物{其是膠態物質或部份溶解之有機物去除，先前主要係使用1呂系之凝集劑。但，眾所周知，叙系凝隼劑例如PAC等，對低濃度原水、低水溫、高驗度原水、鹽類較多之原水凝隼效杲基 … 杲>文果顯者下降，且因處理液中存在鋁，被懷疑對人體有影塑，A田 ’知響故在用於對河川放流或對田地供水 146278.doc 201036921 等之情況，被期望要儘可能地設為低漢度。又，鐵系凝集劑例如⑸等對鋼鐵業之廢液等之利用亦有被研究，但由於因應成為凝集對象之污水中有機物，有變化二氧化矽量之要，且_'損絲大，故若欲將目前之處理設施原狀使用’必須改造控㈣統或關鍵技術，且亦存在資源有限之情況，並非如PAC般之簡單。由於硫酸戴土或綠濛、或氯化鐵等凝集效果較劣，故必須大量使用，但即使大量使用’未必可期待提高凝集效果。因此，使用凝集效果強之凝集劑時若可削減使用4 ’則可使污水處理成本降低，故開發更有效之凝集劑是為人所期望者。尤其是若利用先前所使用之金屬鹽凝集劑，去除溶解之有機物之性能較差，對多量溶解有有機物之污纟，存纟需要藉由使用大量之凝集劑或後處理來分解有機物之缺點。再者，作為問題點，在上述金屬鹽系凝集劑、尤其是含氯凝集劑時，伴隨著上述之電解之處理，例如在農業用廢水處理等之中經常進行之凝集劑處理後，經常會有無法接著進行厭氣性菌處理（細菌滅絕）的事態，是為其缺點。 [專利文獻1]曰本特開平8-117737 [專利文獻2]日本特開2001-54700 [專利文獻3]日本特開2002-45630 [專利文獻4]日本特開2003-275765 [專利文獻5]曰本特開2005-152880 【發明内容】發明所欲解決之問題 146278.doc 201036921 因此’本發明之目的在於提供—種可顯著提高先前所使用之金屬鹽系凝集劑之凝集活性之活性金屬鹽凝集劑。 *又本發明之目的為在製造活性金屬鹽凝集劑時雖施與 • €解’但由於本發明之活性金屬鹽凝集劑所處理之廢液其 . 後不會使厭氣性菌滅絕，故好氣性菌處理自不待言，亦可進行厭氣性菌處理。再者’本發明之目的在於提供一種提高污水之淨化污水之進化方法。 Ο 解決問題之技術手段本發明人等潛心研究，獲得藉由將迄今使用於污水淨化之金屬鹽系凝集劑施與電解處理（通電處理），可達成上、,、目的之知識及見解。述本發明係基於上述知識見解而完成者，提供_種鹽凝集劑或含有該金屬鹽凝集劑之水溶液，予以之活性金屬鹽凝集劑者。电处理〇纟本發明中，作為金屬鹽凝集劑，可舉出的有高屬鹽凝集劑。〇刀子金金屬鹽凝集劑可舉的例有聚氯化鋁石夕鐵系凝集劑。系凝集劑及聚 — M- 一虱化金屬鹽凝集劑為聚氯化鋁系凝集劑時，可舉例的 4.8〜5.5 eV及3.8〜4.2 eV具有光吸收帶者。，、有於金屬鹽凝集劑為聚二氧化矽鐵系凝集劑時，可舉例、 5.9〜6.1 eV之光吸收頻帶之吸光度低於電解處理前者。的有作為電解處理，較佳為直流電解處理。 146278.doc 201036921 又，本發明提供一種活性金屬鹽凝集劑之製造方法，其特徵為.使金屬鹽凝集劑或含有該金屬鹽凝集劑之水溶液存在於具備成為陰陽兩電極之2個電極之容器中，且於兩電極間進行通電。作為上述活性金屬鹽凝集劑之製造方法，其可為包含使用由隔膜區劃陽極側與陰極側之容器進行通電，且回收陽極側之凝集劑之步驟者。通電量較佳為5〜60庫命/g。又，本發明提供一種淨化被處理水的水質淨化方法，包含使技術方案1中記载之活性金屬鹽凝集劑與被處理水接觸之步驟。發明效果本發明之活性凝集劑係藉由對先前所使用之金屬鹽凝集劑或其水溶液，流通以直流或交流電流之電解處理而獲雩“藉由本發明之處理所獲得之活性凝集劑相較於先前之未電解處理之凝集劑’顯示例如超過100倍之格外強之凝集作用。其理由未必明4 ’但可思及的是，若作為電解處理對液體狀凝集劑或凝集劑水溶液通電，卩藉以於液中形成在具正包荷或負電荷之氫氧化金屬鹽系中分子量相對性較大之化合物之聚離子，且藉由該離子所造成之懸浮粒子之電荷的中和；及因該凝集劑分子，由多數懸浮粒子之吸附所引發之架橋等而使凝集力提高；以及亦可獲得溶解有機物之鹽析作用者。本毛明之活性嘁集劑係將先前周知之凝集劑進行電解處 146278.doc 201036921 理，亚使作為該凝集劑之性能顯著提高者，作為凝集劑之使用方法與先前之凝集劑之使用方法並無特別變化，但由於係以更：>、畺之使用而獲得效果者，故對於先前所使用之 • 淨化裝置或淨化過程，可無須作任何變更即可進行利用。 . 根據本發明之活性金屬鹽凝集劑之製造方法，可獲得顯示強凝集作用之金屬鹽凝集劑。又，由於本發明之污水之淨化方法係使用本發明之活性金屬鹽凝集齊卜故相較於使用先前之凝集劑，淨化效率更優良。【實施方式】以下，首先就本發明之活性金屬鹽凝集劑進行說明。本發明之活性金屬鹽凝集劑係電解處理金屬鹽凝集劑或含有該金屬鹽凝集劑之水溶液而成。在本發明中所使用之金屬鹽凝集劑，是指迄今為止例如用於污水處理之金屬鹽凝集劑者。作為如此之金屬鹽凝集劑，可舉例有例如鐵鹽〇 (氯化鐵、硫酸鐵、聚硫酸鐵等）、鋁鹽（硫酸鋁[硫酸礬土] 或聚氯化铭[PAC] ·· [Al2(OH)nCl6-n]m(i把5，邮1〇))、或鈦鹽（氣化鈦等）、硫酸亞鐵（綠礬：FeS〇4.7H2〇)或氯化鐵 (FeClr6H2〇)或以羥基置換硫酸鐵之硫酸基之一部份而成之（[Fe2(0H)n8(S04)33_n/2]m)等之鐵系、還有鐵_二氧化石夕無機高分子之聚矽酸鐵（PSI : [(Si〇2) · (Fe2〇3)i〜3]n)(n=5〇〜2〇〇) 等，但本發明並不限定於此，亦可為迄今為止用於污水處理等者，使用上無特別限制。作為電解處理手段並無限疋’只要使金屬鹽旋集劑或其水溶液存在於電極間並通以 146278.doc 201036921 心 =可’但在本發明'較佳為通以直流電。進 2解處理時，作為含有金屬鹽凝集劑之 : 電解處理時所使…作為如此：用進仃 =用在水中離子化，使水溶液之導電率（離子強度）辦加，物質’例如可舉例的有無機酸，例如鹽酸、硫酸：酸、石肖酸、碳酸箄.古拖缺丰有機酸，例如甲磺酸、甲酸、醋酸、抑* 4豕酸、草酸、對贫-田 t本一甲酉文荨，鹼性物質，例如氫納、氫氧化卸、氨算.於A居201036921 VI. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a flocculating agent for purifying sewage of clean water, waste water, industrial waste water, agricultural waste water, and the like. In particular, it relates to an active aggregating agent having a remarkable effect on sewage containing water-soluble or bulky organic matter and a method for producing the same. [Prior Art] 净化 Purification of wastewater from agricultural waste water, industrial waste water or household waste water containing ordered wet matter or water-soluble matter, or water for forming drinking water (in this specification These are collectively referred to as the purification of sewage), either alone or in combination: by so-called physicalization such as filtration separation treatment, adsorption separation treatment, agglomeration treatment, agglutination floating treatment, electrochemical treatment, etc.: removal of suspended matter or dissolution by hand Impurities, as well as biological means of decomposing and removing substances by utilizing aerobic or degrading biological metabolism. In the physicochemical means, the substance to be removed which is dissolved or (four) or the like is usually a coagulant which is made into a coarse or flocculent state which is suspended or suspended to be separated and removed. The aggregating agent is usually a metal salt such as a sulphate, an iron system, or a town system, and particularly a polymer containing the metal has a high effect. The role of J agglutinating agent, because the turbidity colloid in the sewage is usually negatively charged, so the above metal salt aggregating agent is flocculated by the illusion of the positive particles in water, such as aluminum hydroxy complex. It is to neutralize the electric charge, and to make the horny protein of the colloidal substance or the huminous substance and the organic matter to be used for the analysis, so that the object I46278.doc 201036921 is removed into a lump. By. Previously, as a metal salt-based aggregating agent generally used, mainly using sulfuric acid (alumina: Al2(s〇4)3) or polyaluminized aluminum (PAC: [Al2(OH)nCl6_n]m) (n= 1 to 5, msi 〇), such as aluminum, ferrous sulfate (green strontium: FeS04_7H20) or gasified iron (FeCl3.6H20) or a portion of the sulfate group of ferrous sulfate replaced by a hydroxyl group (polysulfate) Iron-based ferrite (FeSi(O); ~3] η) (η = 50 ~ 200) and so on. Further, in the case where these aggregating agents are used in combination, or a cationic, anionic or nonionic polymeric aggregating agent (aggregation aid) is used alone. As such organic aggregating agents, there are cationic amine-based agglutinating agents such as aniline derivatives, amines such as polyethylenimine, polyamines, and polyacrylamide, which are mainly used for removing waste water or excrement. Or algae such as green algae, green algae, bacteria, etc. The anion in the X 'organic aggregating agent is, for example, a polypropylene crucible, and is particularly used for the pH of the water to be treated from the t to the nature of the test to be used for the cation charged particles containing heavy metal hydroxide. {Listed as pulp mill wastewater, metal machinery factory wastewater, electroplating wastewater, etc. The busy tail is not heterozygous, for example, there is a polycyclic negative r cage; +, · · · Sexually acidic, in the case of Oxygen, etc. It is especially suitable for PH ψ Λ, clay knows wastewater, mineral processing wastewater, etc... The sedimentation of the scallops is promoted and filtered to use a metal salt aggregating agent. The situation is merged, and it also reveals the method of using agglomeration to remove the organic matter in the water of τ in the book. As a means for treating sewage by electrolysis 146278.doc 201036921, a metal electrode is generally used, and cations are supplied to the water to be treated by elution of the electrode during electrolysis. For example, Patent Document 1 '2 uses aluminum or iron. As an electrode. In addition, after the agglomeration of the granules by the electrolysis of the granules by the electrolysis of the granules, the agglomerated granules are formed by the pAc (P/o 3), and the sputum contains the hardly decomposable organic matter. The waste water is firstly decomposed by an aerobic bacteria, and an agglomerating agent containing a metal ion, such as PAC or gasified iron, is added for electrolytic oxidation reduction, thereby promoting the formation of a complex of the metal ion and the hardly decomposable organic substance. : (Patent Document 4), or for the wastewater containing the dioxide, by electrolysis of iron as an electrode, so that a Qiu Song white _ _. The sputum contains an emulsified bismuth-iron agglomerating agent formed in the system to remove the removed substance (Patent Document 5) and the like. However, since the treatment of the sewage by electrolysis is a function of the fouling substance itself contained in the sewage, there is a problem that it is necessary to use a large-sized apparatus or perform electrolysis in the field. Further, in the sewage treatment, in combination with the above-mentioned removal treatment of the floating matter by the metal salt aggregating agent, there is also a decomposition treatment of the organic substance using the fine so-called activated sludge method. For example, in the treatment of agricultural wastewater, etc., it is also often combined with aerobic bacteria treatment and anaerobic bacteria treatment. • As stated in the field, in the case of sewage treatment, it is usually necessary to first remove the sub-organisms made by the agglutinating agent {which is a colloidal substance or a partially dissolved organic substance. Previously, a l-type aggregating agent was mainly used. However, it is well known that a clotting agent such as PAC has a low concentration of raw water, a low water temperature, a high degree of raw water, and a salt with a large amount of raw water. The 文> There is aluminum in the treatment liquid, and it is suspected that it has a shadow on the human body. A field is known to be used for river discharge or water supply to the field 146278.doc 201036921, etc., and it is expected to be as low as possible. In addition, the use of an iron-based aggregating agent such as (5) for the waste liquid of the steel industry has also been studied. However, due to the organic matter in the sewage which is agglomerated, there is a change in the amount of cerium oxide, and _'damage is large. Therefore, if you want to use the current processing facilities in the original state, you must modify the control system or key technologies, and there are also limited resources. It is not as simple as PAC. Since the agglutination effect of sulphuric acid, earthy green, or iron chloride is inferior, it must be used in a large amount, but even if it is used in a large amount, it may not be expected to improve the agglutination effect. Therefore, if the agglutination agent having a strong agglutination effect can be used, the sewage treatment cost can be reduced by reducing the use of 4', and it is desirable to develop a more effective aggregating agent. In particular, if the previously used metal salt aggregating agent is used, the performance of removing dissolved organic matter is poor, and the contamination of a large amount of organic matter is dissolved, and the disadvantage of decomposing the organic substance by using a large amount of aggregating agent or post-treatment is required. Further, as a problem, in the case of the above metal salt-based aggregating agent, particularly a chlorine-containing aggregating agent, it is often treated with the above-mentioned electrolysis treatment, for example, after aggregating agent treatment which is often performed in agricultural wastewater treatment or the like. There is a state in which it is impossible to carry out anaerobic treatment (bacterial extinction), which is a disadvantage. [Patent Document 1] Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION Problems to be Solved by the Invention 146278.doc 201036921 Therefore, the object of the present invention is to provide an active metal salt which can significantly enhance the agglutination activity of a previously used metal salt-based aggregating agent. Agglutinating agent. * Further, the object of the present invention is to apply a solution to the active metal salt aggregating agent, but the waste liquid treated by the active metal salt aggregating agent of the present invention does not cause the anaerobic bacteria to become extinct. The treatment of aerobic bacteria is self-evident, and it can also be treated with anaerobic bacteria. Furthermore, the object of the present invention is to provide an evolutionary method for improving sewage purification of sewage.技术 In order to solve the problem, the inventors of the present invention have made intensive studies and obtained knowledge and insights on the purpose of performing electrolysis treatment (energization treatment) on a metal salt-based aggregating agent that has been used for sewage purification. The present invention has been completed based on the above knowledge, and provides a salt aggregating agent or an aqueous solution containing the metal salt aggregating agent, and the active metal salt aggregating agent. Electric Treatment 〇 In the present invention, as the metal salt aggregating agent, a high-salt agglutinating agent may be mentioned. A knives gold metal salt agglutinating agent may be exemplified by polyaluminum chloride. When the aggregating agent and the poly-M-mono-salt metal salt aggregating agent are polyaluminum chloride-based aggregating agents, those having an optical absorption band of 4.8 to 5.5 eV and 3.8 to 4.2 eV can be exemplified. When the metal salt aggregating agent is a polyferric cerium oxide-based aggregating agent, the absorbance of the light absorption band of 5.9 to 6.1 eV is lower than that of the electrolytic treatment. The electrolytic treatment is preferably a direct current electrolytic treatment. Further, the present invention provides a method for producing an active metal salt aggregating agent, which is characterized in that a metal salt aggregating agent or an aqueous solution containing the metal salt aggregating agent is present in a container having two electrodes which become two electrodes of yin and yang. Medium, and energization between the two electrodes. As a method for producing the above-mentioned active metal salt aggregating agent, it may be a step of using a container in which the anode side and the cathode side are partitioned by a separator, and recovering the aggregating agent on the anode side. The power supply is preferably 5 to 60 life/g. Moreover, the present invention provides a water purification method for purifying treated water, comprising the step of contacting the active metal salt aggregating agent described in claim 1 with the water to be treated. EFFECTS OF THE INVENTION The active aggregating agent of the present invention is obtained by electrolytic treatment of a metal salt aggregating agent or an aqueous solution thereof which has been used previously, by direct current or alternating current, "the active aggregating agent obtained by the treatment of the present invention is compared. The previously unelectrolyzed aggregating agent 'shows, for example, an exceptionally strong agglomeration of more than 100 times. The reason for this is not necessarily 4', but it is conceivable that if the liquid aggregating agent or the aqueous solution of the aggregating agent is energized as an electrolytic treatment,聚 a polyion formed by forming a compound having a relatively large molecular weight in a metal hydroxide having a positively or negatively charged metal in a liquid, and neutralizing the charge of the suspended particles by the ion; The aggregating agent molecule enhances the cohesive force by bridging caused by adsorption of a plurality of suspended particles, and can also obtain a salting-out effect of dissolved organic matter. The active agent of the present invention is electrolyzed by a previously known aggregating agent. 146278.doc 201036921, As a significant improvement in the performance of the agglutinating agent, as a method of using the agglutinating agent and the previous agglutinating agent There is no particular change in the method of use, but since the effect is obtained by using: >, 畺, the purification device or the purification process previously used can be utilized without any change. In the method for producing the active metal salt aggregating agent of the invention, a metal salt aggregating agent exhibiting strong agglutination can be obtained. Further, since the method for purifying sewage according to the present invention uses the active metal salt of the present invention to agglutinate, compared with the use of the prior The aggregating agent is more excellent in purification efficiency. [Embodiment] Hereinafter, the active metal salt aggregating agent of the present invention will be described. The active metal salt aggregating agent of the present invention is an electrolytically treated metal salt aggregating agent or a metal salt aggregating agent. The metal salt aggregating agent used in the present invention refers to a metal salt aggregating agent which has heretofore been used, for example, for sewage treatment. As such a metal salt aggregating agent, for example, iron salt strontium (chlorine) can be exemplified. Iron, iron sulfate, polyferric sulfate, etc., aluminum salt (aluminum sulfate [sulphate] or polychlorinated [PAC] · · [Al2(OH)nCl6-n]m (i put 5 1)), or titanium salt (titanized gas, etc.), ferrous sulfate (green strontium: FeS 〇 4.7H2 〇) or ferric chloride (FeClr6H2 〇) or a part of the sulphate group of ferrous sulfate replaced by hydroxy An iron-based ([Fe2(0H)n8(S04)33_n/2]m), iron-based, iron-phosphorus oxide, inorganic polymer, polyferric acid (PSI: [(Si〇2) (Fe2〇3)i~3]n) (n=5〇~2〇〇), etc., but the present invention is not limited thereto, and may be used for sewage treatment and the like, and is not particularly limited in use. As an electrolytic treatment means, it is infinitely arbitrarily 'as long as a metal salt rotator or an aqueous solution thereof is present between the electrodes and is passed through 146278.doc 201036921 heart = can be 'but in the present invention' is preferably a direct current. In the case of the second solution treatment, it is used as a metal salt aggregating agent: in the case of electrolytic treatment, as the case: using ionization = ionization in water, the conductivity (ionic strength) of the aqueous solution is added, and the substance 'for example, for example There are inorganic acids, such as hydrochloric acid, sulfuric acid: acid, oxalic acid, barium carbonate. Ancient toxins, such as methanesulfonic acid, formic acid, acetic acid, tetrahydroic acid, oxalic acid, Hyperthyroidism, alkaline substances, such as hydrogen, hydrogen hydroxide, ammonia, in A

電解液之漠度通Γ為。：氯化鉀、氯化鈉等。、常為0.1 mol/L〜8 m〇1/L左右，較佳為〇 i 雷条^容後述。在本說明書中，亦有將電解處理表現為通電處理之情況，將兩者作為同義使用。再者，作為在本發明中所使用之金屬鹽凝集劑，較佳為化紹系凝集劑（PAC)及鐵-二氧切無機高分子之聚石夕The infiltration of the electrolyte is overnight. : Potassium chloride, sodium chloride, and the like. It is usually about 0.1 mol/L to 8 m〇1/L, preferably 〇 i. In the present specification, the electrolytic treatment is also expressed as a power-on treatment, and the two are used synonymously. Further, as the metal salt aggregating agent used in the present invention, it is preferred that the agglomerating agent (PAC) and the iron-dioxon inorganic polymer are collected.

二氧切鐵系凝集劑)。聚氯化銘系凝集劑根據電處理’於4.8〜5.5 eV及3·8〜4 2 eV具有光吸收帶。此處，具有光吸收帶是指將含有PAC之溶液（根據場合而定，以水等，㈣進行稀釋)藉由分光光度計測定光吸收光譜時，在5亥乾圍之吸光度大於未進行電解處理者。由於we在施 :電解處理前，於該範圍不具有光吸收帶，故可與經施加電解處理者區別。X，從後述之實施例可知，於上述範圍具$光吸收帶之PAC係可提高凝集效率者。又，光吸收帶之範圍根據作為原料使用之金屬鹽凝集劑而有不同，例如 M6278.doc •10- 201036921 為5_2〜5.4 eV及4_0〜4·2 eV之範圍’或為4·9…及3 9 ev附近。出現該光吸收體之增加係H〇M〇_LUM〇之遷移所造成者’或因微量雜質有可能於能階產生略微之變化，將此反映者。總之，該範圍之光吸收帶之出現係與所獲得之活性金屬鹽凝集劑之凝集活性之提高一致。又，在本發明中’作為金屬鹽凝集劑亦可使用聚二氧化矽鐵系凝集劑（鐵-二氧化矽無機高分子之聚合矽酸鐵， psi)。此情況，由於活性金屬鹽凝集劑在5 9〜6 i ev之光吸收頻帶之吸光度相較於電解處理前暫時增加，若繼續電解處理，則該範圍之吸光度會降低，故可與未施與電解處理者區別。又，本發明之活性金屬鹽凝集劑較佳為含於其中之氯離子濃度較低者。若存在氯離子，則會阻礙凝集能，但本發明之活性金屬鹽凝集劑係因進行電解處理，氯離子因電解反應而以氯氣放出，從而使氯離子濃度降低，藉此提高凝集能。本發明之活性金屬鹽凝集劑可用於本發明之水質淨化方法。本發明之水質淨化方&包含使上述之本發明活性金屬鹽凝集劑與被處理水接觸之步驟。在本發明之水質淨化方法中’成為對象之被處理水並無特別限制，可舉例的有生活廢水或產業廢水，例如最終處分場浸出水、垃圾焚燒廢水、下水道處理水、糞尿處理水、半導體工廠廢水、電子工廠廢水、電鍍工廠廢水、水 146278.doc -11 - 201036921 產加工廠廢水、食品飲料製造工廠廢水等之工廠廢水、礦業廢水、農業廢水、畜產廢水、潔淨水處理廢水此等之在處理時需要淨化者。由於本發明之活性金屬鹽凝集劑使蛋白質成份凝集之效果優良，故尤其是適用於將含有蛋白質性質之被去除成份（亦包含食品或血液成份）之廢水作為被處理水者。本發明之水質淨化方法包含使本發明之活性金屬鹽凝集劑與被處理水接觸之步驟。作為使活性金屬鹽凝集劑與被處理水接觸之方法，無特別限制，可舉例為例如將被處理水與活性金屬鹽凝集劑混合之方法。不管是何種方法，均宜使活性金屬鹽凝集劑與被處理水連續性接觸。作為使其接觸之方法，如上所述，除使活性金屬鹽凝集劑與被處理水混合之方法以外，亦可例如在以纖維等形成之袋狀體中或片狀體之間，置入本發明之活性金屬鹽凝集劑，使其浮於'或沉入被處理水而使用。又，亦可在配設於廢水之淨化裝置之水循環路徑之過濾槽中，配置本發明之活性金屬鹽凝集劑而使用。此時，亦可併用迄今為止為淨化被處理水所使用之過濾器或活性碳、其他過遽劑等。其次，就本發明之活性金屬鹽凝集劑之製造方法進行說明。本發明之活性金屬鹽凝集劑之製造方法包含使金屬鹽凝集劑或含有該凝集劑之水溶液存在於具備成為陰·陽兩電極之2個電極之容器中，並於兩電極間進行通電之步驟，即，本發明之活性金屬鹽凝集劑之製造方法包含將成為 146278.doc -12- 201036921 陰·陽兩電極之2個電極，浸潰於金屬鹽凝集劑或含有該凝集劑之水溶液中，並於兩極間進行通電之步驟。作為水/谷液，較佳為電解液。電解液為如上所述者。作為電解手段並無限定，使金屬鹽凝㈣或其水溶液存在於電極間並通以錢或交流電即可。在本發明巾，通電較佳為藉由施加直流電壓而達成者。Dioxo iron-based aggregating agent). The polychlorinated agglutinating agent has a light absorbing band according to the electric treatment of 4.8 to 5.5 eV and 3·8 to 4 2 eV. Here, the light absorption band means that when the light absorption spectrum is measured by a spectrophotometer by using a solution containing PAC (diluted by water or the like according to the case), the absorbance at 5 Å is higher than that without electrolysis. Processor. Since we do not have a light absorbing tape in this range before the electrolysis treatment, it can be distinguished from those subjected to electrolytic treatment. X, as will be understood from the examples described later, the PAC system having the light absorption band in the above range can improve the aggregation efficiency. Further, the range of the light absorption band differs depending on the metal salt aggregating agent used as a raw material, for example, M6278.doc •10-201036921 is a range of 5_2 to 5.4 eV and 4_0 to 4·2 eV' or 4·9... and 3 9 ev nearby. The occurrence of the increase in the light absorber is caused by the migration of H〇M〇_LUM〇 or the slight change in the energy level due to trace impurities, which is reflected. In summary, the appearance of the light absorption band in this range is consistent with the increase in the agglutination activity of the active metal salt aggregating agent obtained. Further, in the present invention, as the metal salt aggregating agent, a polyferric ruthenium iron-based aggregating agent (polymerized iron ruthenate of iron-cerium oxide inorganic polymer, psi) may be used. In this case, since the absorbance of the active metal salt aggregating agent in the light absorption band of 5 9 to 6 i ev is temporarily increased compared with that before the electrolytic treatment, if the electrolytic treatment is continued, the absorbance of the range is lowered, so that it may be Electrolytic processors differ. Further, the active metal salt aggregating agent of the present invention preferably has a lower chlorine ion concentration contained therein. If chloride ions are present, the aggregation energy is inhibited. However, the active metal salt aggregating agent of the present invention is subjected to electrolytic treatment, and chloride ions are released by chlorine gas due to the electrolysis reaction, thereby lowering the chloride ion concentration and thereby increasing the aggregation energy. The active metal salt aggregating agent of the present invention can be used in the water purification method of the present invention. The water purifying agent of the present invention comprises the step of bringing the above-mentioned active metal salt aggregating agent of the present invention into contact with the water to be treated. In the water purification method of the present invention, the water to be treated is not particularly limited, and examples thereof include domestic wastewater or industrial wastewater, such as final site leaching water, garbage incineration wastewater, sewage treatment water, waste water, and semiconductor. Factory wastewater, electronic factory wastewater, electroplating factory wastewater, water 146278.doc -11 - 201036921 Factory wastewater, mining wastewater, agricultural wastewater, livestock wastewater, clean water treatment wastewater, etc. A purifier is required for processing. Since the active metal salt aggregating agent of the present invention has an excellent effect of aggregating a protein component, it is particularly suitable for use as a water to be treated as a waste water containing a protein-containing component (including a food or a blood component). The water purification method of the present invention comprises the step of bringing the active metal salt aggregating agent of the present invention into contact with the water to be treated. The method of bringing the active metal salt aggregating agent into contact with the water to be treated is not particularly limited, and for example, a method of mixing the water to be treated and the active metal salt aggregating agent can be exemplified. Regardless of the method, the active metal salt aggregating agent is preferably in continuous contact with the water to be treated. As a method of bringing it into contact, as described above, in addition to the method of mixing the active metal salt aggregating agent with the water to be treated, for example, it may be placed in a bag-like body formed of fibers or the like or between the sheet-like bodies. The active metal salt aggregating agent of the invention is used to float or sink into the treated water. Further, the active metal salt aggregating agent of the present invention may be disposed in a filtration tank disposed in a water circulation path of a purification apparatus for wastewater. In this case, a filter or activated carbon used for purifying the water to be treated, other over-twisting agents, and the like may be used in combination. Next, a method of producing the active metal salt aggregating agent of the present invention will be described. The method for producing an active metal salt aggregating agent according to the present invention comprises the steps of allowing a metal salt aggregating agent or an aqueous solution containing the aggregating agent to be present in a container having two electrodes which are electrodes of both the anode and the cathode, and energizing between the electrodes That is, the method for producing the active metal salt aggregating agent of the present invention comprises: immersing two electrodes of 146278.doc -12-201036921 yin and yang electrodes in a metal salt aggregating agent or an aqueous solution containing the aggregating agent, And the step of energizing between the two poles. As the water/gluten solution, an electrolyte solution is preferred. The electrolyte is as described above. The electrolysis means is not limited, and the metal salt may be condensed (IV) or an aqueous solution thereof may be present between the electrodes and may be supplied with money or alternating current. In the towel of the present invention, energization is preferably achieved by applying a DC voltage.

“由於經活性化處理之金屬鹽凝集劑或其水溶液係與通電 =量（庫侖量）成比例般之接t電化學變化，故雖在通電電 f增大的同時’凝集活性提高，但亦有若超過—定值則凝卞ί·生降低之情況。可考慮其係過量地接受電氣分解，因 ⑽暫時形成之凝集力強之狀態’進步由於電解而使分子接受分解’從而使凝集活性降低者。通電量亦可根據使用之凝集劑之種類或濃度而不同，可參考後述之實施例等’利用預備試驗而容易求得適當之電解處理條件。例如作為通電#，合計通電量較佳為5〜6g庫侖&，更佳為$〜⑼ 庫心。此處’通電量係以作為原料使用之金屬鹽凝集劑之每1 g之庫侖量表示。即’增加使用之金屬鹽凝集劑之量之情況’藉由使電流量增加或延長通電時間，可獲得凝集效率相同之活性金屬鹽凝集劑。若上述通電量不足5庫侖則存在凝集活性效果不會提高之情況，另一方面，通電量回於6G庫命/g ’凝集活性效果亦不會作更高升。進行通電處理之時間可，從後述之實施例中 ’在通電量為上述範圍内之時間可知’本發明之活性金屬鹽凝集即劑 146278.doc 201036921 /4.8 5.5 eV及3 8〜4 2 eV具有光吸收帶之情$兄時由於其凝集效率提高，故較佳為實施通電處理，直至於4 8:5、5 Γ^3·8〜4·2 ev具有光吸收帶。此情況，亦可在通電處理取4烈時’抽樣試料之一部份測定吸光度，—面確認在上述範圍内是否會出現光吸收帶，__面進行通電處理。作為=解條件，首先必須流動以一定之電流，因此必$ 之通電置係根據電極材料之種類、或處理之金屬鹽凝集劑、ώ種類纟之有無等而定。通常若電壓過低，則電流不會桃動，又，電壓過高由於會導致過度之水之電解，故不 ❹ 佳。又’為避免電壓變過高，亦存在宜添加驗金屬鹽，例如氯化鉀、氯化納等作為助劑之情況。即較佳為使用電解液。々又，作為電極材料’直流之情況下’陰極為鐵或錄、碳等之導電體材料即可，陽極在考慮金屬之溶出，溶出亦= 妨之情況下，鋁或鐵即可，欲避免金屬溶出之情況，較佳"Because the activated metal salt aggregating agent or its aqueous solution is electrochemically changed in proportion to the amount of electricity (the amount of coulomb), the agglutination activity is improved while the energization electric f is increased, but If it exceeds the value, it will be reduced. It can be considered to be excessively subjected to electrical decomposition, because (10) the state of strong agglutination temporarily formed, 'progressively decomposes the molecule due to electrolysis', thereby agglutinating activity The amount of energization may vary depending on the type or concentration of the aggregating agent to be used, and it is easy to obtain appropriate electrolytic treatment conditions by referring to the examples and the like described later. For example, as the energization #, the total amount of energization is preferably 5~6g Coulomb &, more preferably $~(9) core. Here, the amount of energization is expressed by the amount of coulomb per 1 g of the metal salt aggregating agent used as a raw material. In the case of the amount, an active metal salt aggregating agent having the same agglutination efficiency can be obtained by increasing the amount of current or prolonging the energization time. If the above-mentioned energization amount is less than 5 coulombs, there is an agglutination activity effect. On the other hand, the power supply is returned to the 6G storage life / g 'aggregation activity effect will not be higher. The time for energization processing can be, in the embodiment described later, the power supply amount is the above range. The time inside can be known as 'the active metal salt agglutination agent of the present invention 146278.doc 201036921 /4.8 5.5 eV and 3 8~4 2 eV have a light absorption band. Since the aggregation efficiency is improved, it is preferred to implement the current supply. After treatment, it has a light absorption band at 4 8:5, 5 Γ^3·8~4·2 ev. In this case, the absorbance can also be measured in one part of the sample sample when the power treatment is taken 4 times. Whether or not the light absorbing tape appears in the above range, and the __ surface is energized. As the = solution condition, it is necessary to first flow a certain current, so that the energization is required to be based on the type of the electrode material or the metal salt of the treatment. Usually, if the voltage is too low, the current will not move, and if the voltage is too high, it will lead to excessive electrolysis of water, so it is not good. High, there should also be added A salt, such as potassium chloride or sodium chloride, is used as an auxiliary agent. It is preferred to use an electrolyte. Further, as an electrode material, in the case of a direct current, the cathode is an electrical material such as iron or carbon or carbon. Yes, the anode is considering the dissolution of the metal, and the dissolution is also possible. In the case of aluminum or iron, it is preferable to avoid the dissolution of the metal.

為使用白金等之貴金屬或錄有白金等之金屬等，另外使用碳等亦可。 D '再者，在交流電解中，欲避免金屬之溶出之情況，較佳為兩極皆使用白金電極等。再者，電解溫度無特別限定，在室溫下即可。本發明之利用電解之活性化處理對金屬鹽凝集劑整體有政’特別對包含縮聚型金屬高分子之金屬鹽凝集劑、尤其 AC或PSI有顯著效果。其理由未必明確，但可預想為是否為因電解產生PAC或psi之分子之切斷，且產生金屬之水合 146278.doc • 14- 201036921 氫凝膠化、及離子量之增大。 §亥荨現象隨著電解之丨隹# ι , 仃_出現於光吸收光譜。即在 PAC之情形下，於4 8〜5 5 (无其疋5.3)eV及3.8〜4.2(尤其是 4_13)eV，光吸收光譜之峰值出現。又，在PSI之情形；， .隨著電解處理時間之經過，使5.9〜61心4〇〜43 ^之光吸收帶產生變化。在PAC時，因電解新出現之光吸收峰值之值雖會達到最大，但與凝集活性之最大值大致一致。在〇 psi之情形下，增加光吸收帶之峰值強度時，凝集性能提馬。因此’即使測定光吸收光譜，亦可充分確認本發明之電解處理之適當之條件。又，在本發明之活性金屬鹽凝集劑之製造方法中，亦可為包含使用由隔膜區劃陽極側與陰極側之容器進行通電，而回收陽極側之凝集劑之步驟者。在本發明之活性金屬鹽、是集J之製造方法中，由於考慮陽極反應會引起凝集性能之提阿，故藉由回收陽極側之凝集劑，可獲得凝集性能進 Q —步提高者。再者，作為所使用之隔膜，可使用浸透膜、碳纖維之板等。藉由本發明之活性金屬鹽凝集劑之製造方法所獲得之活 1"生金屬鹽凝集劑可原狀添加至應淨化之水而使用，但，亦可使用例如藉由離心分離等使水分減少者，或凍結乾燥者。貫施例以下，藉由實施例更詳細地說明本發明。又，當然本發 146278.doc -15- 201036921 明之範圍並非限定於下述之實施例中。實施例1 作為電解裝置，係使用以下者。使用在内徑1 8 mm、高度50 mm之圓柱狀玻璃容器中，設置有白金線[直徑〇·3 mm、長度12·5 mm(有效長度40 mm)、電極間距離1 3 mm]作為電極之電解槽。電解處理之條件如下所示。施加電壓直流45 V(以下）電流值 3 0 m A(定電流控制）In order to use precious metals such as platinum or metals such as platinum, carbon or the like may be used. D' Further, in the case of alternating current electrolysis, in order to avoid the elution of the metal, it is preferable to use a platinum electrode or the like for both poles. Further, the electrolysis temperature is not particularly limited and may be at room temperature. The activation treatment by electrolysis of the present invention has a remarkable effect on the metal salt aggregating agent as a whole, particularly for a metal salt aggregating agent containing a polycondensation type metal polymer, particularly AC or PSI. The reason for this is not necessarily clear, but it is expected that it is a cleavage of a molecule which produces PAC or psi by electrolysis, and hydration of a metal is produced. 146278.doc • 14- 201036921 Hydrogen gelation and an increase in the amount of ions. § The phenomenon of 荨随着随着随着随着电解电解电解电解电解电解电解电解电解电解电解电解电解电解That is, in the case of PAC, at 4 8 to 5 5 (no 疋 5.3) eV and 3.8 to 4.2 (especially 4_13) eV, the peak of the light absorption spectrum appears. Also, in the case of PSI;, with the passage of the electrolytic treatment time, the light absorption band of 5.9~61 heart 4〇~43^ is changed. In the case of PAC, the peak value of the light absorption peak due to electrolysis is maximized, but it is approximately the same as the maximum value of the agglutination activity. In the case of 〇 psi, when the peak intensity of the light absorption band is increased, the agglutination performance is lifted. Therefore, even if the light absorption spectrum is measured, the appropriate conditions for the electrolytic treatment of the present invention can be sufficiently confirmed. Further, in the method for producing an active metal salt aggregating agent of the present invention, the step of charging the container on the anode side and the cathode side by the separator may be used to recover the aggregating agent on the anode side. In the production method of the active metal salt of the present invention and the formation of J, since the agglutination performance is caused by the anode reaction, the agglutination performance of the anode side can be recovered. Further, as the separator to be used, a permeation film, a carbon fiber board or the like can be used. The raw metal salt agglutinating agent obtained by the method for producing an active metal salt aggregating agent of the present invention can be used as it is to be purified as it is, but it is also possible to reduce the amount of water by centrifugation or the like, for example. Or freeze the dryer. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail by way of examples. Further, of course, the scope of the present invention is not limited to the embodiments described below. Example 1 As the electrolysis device, the following were used. In a cylindrical glass container with an inner diameter of 18 mm and a height of 50 mm, a platinum wire [diameter 〇·3 mm, length 12·5 mm (effective length 40 mm), distance between electrodes 13 mm] is provided as an electrode Electrolytic cell. The conditions of the electrolytic treatment are as follows. Applied voltage DC 45 V (below) Current value 3 0 m A (constant current control)

水溫 23 °C 處理時間 90分通電量 16庫侖/g 於上述電解裝置加入聚氯化鋁（PAC : [Al2(OH)nCl6_n]m) (n=l〜5、10)(北海道曹達株式會社製）10 mL，通電並進行電解處理，而獲得作為活性化金屬鹽凝集劑之活性化 PAC。將如上所得之1 mL活性化PAC與1 mL水混合，作為試料。另外，將未進行電解處理之PAC設為比較例1。將50 mL KC1水溶液（濃度100 mM)加入至燒杯，其次，加入2 mL球蛋白水溶液（濃度5 0 μΜ)，充分予以搜拌。其次，將上述所得之試料添加至燒杯，以400 rpm攪拌1分鐘，並將於燒杯中所生成之沉澱在靜置0分鐘、5分鐘、10 分鐘、30分鐘、60分鐘、90分鐘及120分鐘後，以肉眼觀察。 146278.doc -16- 201036921 結果係顯不於圖1中力阁]由 T在圖1中’ A1〜Α7、Β1〜Β7顯示分別靜置〇分鐘、5分鐘、1 〇八於 m八λα 鐘10刀鐘、30分鐘、60分鐘、90分鐘及120分鐘後之比較作"之結果、實施例^之紝果。 • 在比較例1中，將PAC試料溶液添加至燒：内之球蛋白溶液後，溶液立即開始白濁，其後，至3〇分鐘左右，雖未 “濁之溶液之顏色中觀察到較大變化，但觀察到經過％ ^ :後Ο有絮狀之蛋白f成份凝集體沉殿至燒杯之底部〇 “。若進一步放置，則60分鐘後，絮狀體變得清晰’ 120分鐘以後沉澱凝集體^ ^ ^ ^ w兄父化。活性金屬鹽凝隼鈉添加之後立即變白濁，但 ” 破果展度較比較例1更濃，5 为鐘後在燒杯之底部可觀察到沉澱物。 :後’在1〇分鐘時溶液變透明，凝集體全部沉澱至燒杯若經過40分鐘，則其後沉殿凝集體之沉殿層之高又亚未有變化。相較於該結疋〜見貫施例1之凝集體的之凝集活性高於比較例i之凝集。 0 實施例2 替換球蛋白水溶液，僮 η〜及使用白蛋白水溶液（濃度50 μΜ)，進灯與貫施m同樣之試驗。 .㈣行料，將其料轉；2 之 •巾。I、料比較例2。結果顯示於圖2 浐1〇、，C1〜C7、D1〜D7顯示分別靜置0分鐘、5分釦、10为鐘、30分鐘、60分鐘、9 較例2之結果、實施例2之結果。、里“童後之比液:若將PSI試料添加至燒杯内之白蛋白水溶、立即產生白濁’但若繼續放置則直接沉澱凝 146278.doc 201036921 集，溶液變成透明（ci)。其後，於燒杯之底部之凝集體未發現有變化，但經過30分鐘後，凝集體浮游至水面。浮游凝集體繼續增加直至90分鐘，120分鐘以後則穩定化。另一方面，在實施例2中，攪拌後立即發現凝集體，但凝集結束（沉澱物之不再增加時）最遲需要30分鐘左右。但，凝集濃度高，未觀察到絮狀浮游。綜合實施例1及2、比較例1及2顯示於表1。表1 向球蛋白水溶液、白蛋白水溶液添加了 PAC時之比較含有蛋白質 PAC之條件凝集絮片形成開始開始密度球蛋白 PAC 添加後立即低 50分鐘左右電氣處理PAC 添加後立即 A 5分鐘左右白蛋白 PAC 添加後立即低 1分鐘左右電氣處理PAC 添加後立即 1分鐘左右 [註]如圖1、2所示，添加有經電氣處理PAC者，沉澱凝集體之顏色更白，凝集體之密度或凝集之程度增高。實施例3 調查電解處理與光吸收光譜之關係。與實施例1相同，將聚氯化鋁電解處理，在電解處理開始前、電解處理開始5分鐘後、電解處理開始10分鐘後、其後每隔10分鐘直至90分鐘，抽樣試料，並以自記式分光光度計（株式會社日立之製作所製：U-3500)測定光吸收光譜。將結果顯示於圖3。從圖3可知，若進行電解處理，則在紫外可視光區域之全域内吸光度同樣增加，但隨著電解處理時間之經過，於 146278.doc •18- 201036921 5.2〜5.4 eV及4·〇〜4 2 eV附近出現光吸收帶。义於圖4顯*從在料各個日夺間處理之PAC之光吸收光譜’減算初期光吸收光譜，並求得因電解處理而變化之光吸收增加成份者。根據該圖，發現於4.8〜5.5 eV(尤其是5 3 eV:及3.8〜4.2 eV(尤其是4l3 eV)附近，產生能量之峰值。該等之峰值係隨著電解處理時間而增加，但在—定時間後 Ο 飽和，並有因進—步持續之處理而轉變成減少之趨勢。實施例4 在與實施例1相同之電解裝置中，置人11 mL聚二氧化石夕鐵系凝集劑（PSI : [(Si〇2).(Fe2〇3)i〜3]n)(n=5〇〜2〇〇)(南海化學工業株式會社製)’使用與實施例1相同之裝置，進行30 ^之通電，進行電解處理。電解處理之時間為進行360分鐘’從而獲得作為活性化金屬鹽凝集劑之活性化psi。通電量為59庫侖/g。Water temperature: 23 °C, treatment time, 90 minutes, electricity supply, 16 coulombs/g, polyaluminium chloride (PAC: [Al2(OH)nCl6_n]m) (n=l~5, 10) was added to the above electrolyzer (Hokkaido Soda Co., Ltd.) 10 mL, energized and subjected to electrolytic treatment to obtain an activated PAC as an activated metal salt aggregating agent. 1 mL of the activated PAC obtained above was mixed with 1 mL of water as a sample. Further, the PAC which was not subjected to electrolytic treatment was referred to as Comparative Example 1. 50 mL of KC1 aqueous solution (concentration 100 mM) was added to the beaker, and secondly, 2 mL of globulin aqueous solution (concentration of 50 μM) was added, and the mixture was fully mixed. Next, the sample obtained above was added to a beaker, stirred at 400 rpm for 1 minute, and the precipitate formed in the beaker was allowed to stand for 0 minutes, 5 minutes, 10 minutes, 30 minutes, 60 minutes, 90 minutes, and 120 minutes. Afterwards, observe with the naked eye. 146278.doc -16- 201036921 The results are not shown in Fig. 1] by T in Figure 1 'A1~Α7, Β1~Β7 are shown to stand for 〇 minute, 5 minutes, 1 〇8 in m 八λα Comparison of 10 knives, 30 minutes, 60 minutes, 90 minutes, and 120 minutes, and the results of the example ^. • In Comparative Example 1, after the PAC sample solution was added to the globulin solution in the burn: the solution immediately became cloudy, and thereafter, it was about 3 minutes, although no significant change was observed in the color of the turbid solution. However, it was observed that after % ^ :, there was a flocculent protein f component that condensed the temple to the bottom of the beaker. If placed further, after 60 minutes, the floc becomes clear. After 120 minutes, the precipitated aggregates ^ ^ ^ ^ w brothers. Immediately after the addition of the active metal salt, sodium turbidity became cloudy, but the fruit break was more concentrated than that of Comparative Example 1, and 5 minutes later, a precipitate was observed at the bottom of the beaker. : After 'the solution became transparent at 1 minute. If all the aggregates are precipitated into the beaker for 40 minutes, then the height of the sinking layer of the sinking pool will not change. Compared with the agglutination activity of the agglomerate of the crucible It is higher than the agglutination of Comparative Example i. 0 Example 2 Replace the globulin aqueous solution, the child η~ and the aqueous albumin solution (concentration 50 μΜ), and the same test as the light application. (4) Feeding the material and transferring the material 2, towel, I, material comparison example 2. The results are shown in Fig. 2 浐1〇, C1~C7, D1~D7 are displayed respectively for 0 minutes, 5 minutes, 10 minutes, 30 minutes, 60 minutes. 9, the result of the second example, the result of the example 2, the "children's ratio liquid: if the PSI sample is added to the beaker, the albumin is dissolved in water, and immediately becomes white turbid", but if it continues to be placed, it directly precipitates 146278. Doc 201036921 set, the solution becomes transparent (ci). Thereafter, no change was observed in the agglomerates at the bottom of the beaker, but after 30 minutes, the agglomerates floated to the surface. The floating aggregate continues to increase until 90 minutes, and is stabilized after 120 minutes. On the other hand, in Example 2, the aggregate was found immediately after the agitation, but the end of the agglutination (when the precipitate did not increase) required about 30 minutes at the latest. However, the agglutination concentration was high and no flocculation was observed. General Examples 1 and 2, and Comparative Examples 1 and 2 are shown in Table 1. Table 1 Comparison of the addition of PAC to aqueous globulin solution and albumin aqueous solution. Conditions for protein-containing PAC. Aggregation of floc formation begins. Immediately after the addition of density globulin PAC, 50 minutes after electrical treatment, PAC is added immediately after addition of A5 minutes. Immediately after the PAC is added, the PAC is treated for about 1 minute, and the PAC is added immediately after 1 minute. [Note] As shown in Fig. 1 and 2, when the PAC is treated with electric treatment, the color of the precipitated aggregate is whiter, and the density or agglutination of the aggregate The degree is increasing. Example 3 The relationship between electrolytic treatment and light absorption spectrum was investigated. In the same manner as in Example 1, the polyaluminum chloride was electrolytically treated, and the sample was sampled before the start of the electrolytic treatment, 5 minutes after the start of the electrolytic treatment, 10 minutes after the start of the electrolytic treatment, and every 10 minutes until 90 minutes thereafter. A spectrophotometer (manufactured by Hitachi, Ltd.: U-3500) was used to measure the light absorption spectrum. The results are shown in Figure 3. As can be seen from Fig. 3, if electrolytic treatment is performed, the absorbance in the ultraviolet visible light region is also increased, but as the electrolysis treatment time passes, it is 146278.doc •18-201036921 5.2~5.4 eV and 4·〇~4 2 A light absorption band appears near eV. It is shown in Fig. 4 that the light absorption spectrum of the PAC of the PAC treated in each day is reduced, and the light absorption spectrum at the initial stage is reduced, and the light absorption increasing component which is changed by the electrolytic treatment is obtained. According to the figure, it is found that a peak of energy is generated in the vicinity of 4.8 to 5.5 eV (especially 5 3 eV: and 3.8 to 4.2 eV (especially 4l3 eV). The peaks are increased with the electrolytic treatment time, but in - After a certain period of time, Ο is saturated, and there is a tendency to decrease due to continuous processing. Example 4 In the same electrolysis apparatus as in Example 1, 11 mL of polychlorinated iron oxide agglomerating agent was placed. (PSI: [(Si〇2). (Fe2〇3)i~3]n) (n=5〇~2〇〇) (manufactured by Nankai Chemical Industry Co., Ltd.) was carried out using the same apparatus as in Example 1. The electrolysis treatment was carried out at 30 °, and the electrolytic treatment was carried out for 360 minutes to obtain an activated psi as an activated metal salt aggregating agent. The amount of electricity was 59 coulombs/g.

於試管中置入2.5 mL純水及〇] mL球蛋白水溶液（濃度綱μΜ)，《分㈣。其二欠，加入！社如上所得之活性化 PSI ’充分攪拌。X，將未進行電解處理者作為比較實驗進行。添加活性化PSIi^拌之，立即以肉眼觀察試管，其後’靜置5分鐘、！〇分鐘、3〇分鐘、6()分鐘、％分鐘、 1/〇分鐘、刚分鐘、240分鐘及36〇分鐘後，以肉眼觀察試管内所生成之沉澱。將結果顯示於圖5。在圖5中，在各個照片下記载靜置之時間，各照片之左側之試管顯示使用未接受電解處理之 PS!之實驗的結果’各照片之右側之試管顯示使用經则分 M6278.doc 19- 201036921 鐘電解處理之PSI的實驗之結果。從圖5可知，未進行處理者與靜置時間無關，幾乎未顯示凝集。另—方面、解 360分鐘之電解處理者，無關靜置時間，添加後每個^Place 2.5 mL of pure water and 〇] mL globulin aqueous solution (concentration μΜ) in the test tube, sub-division (4). The second owe, join! The activated PSI' obtained as above was sufficiently stirred. X, the person who did not perform the electrolytic treatment was carried out as a comparative experiment. Add the activated PSIi^ and immediately observe the test tube with the naked eye, then let stand for 5 minutes! The precipitate formed in the test tube was visually observed after 〇 minute, 3 〇 minutes, 6 () minutes, % minutes, 1/〇 minutes, just minutes, 240 minutes, and 36 minutes. The results are shown in Figure 5. In Fig. 5, the time of standing is described under each photograph, and the test tube on the left side of each photograph shows the result of the experiment using the PS which has not been subjected to electrolytic treatment. 'The test tube on the right side of each photograph shows the use of the passage point M6278.doc 19 - 201036921 The result of the experiment of PSI electrolysis. As can be seen from Fig. 5, the person who did not perform the treatment showed almost no agglutination regardless of the standing time. Another aspect, the solution of 360 minutes of electrolytic treatment, regardless of the rest time, after adding each ^

均立即產生凝集體，隨著時間經過而沉澱。 S 實施例5 調查電解處理與光吸收光譜之關係。一與實施例3同樣地，將psi電解處理，在電解處理開始前、電解處理開始 5、1〇、2〇、3〇、45、6〇、9〇、12\、° 150、180、210、240、380、440分鐘後抽樣試料，並以自〇 «己式刀光光度計（株式會社曰立製作所製：U—3500)測定光吸收光譜。又’由於光吸收度高’故測定係將試料稀釋成數千倍而進行。將結果顯示於圖6。蛛PSI原本於5·9〜6」eV附近與41〜45 eV附近具有光吸收可，但該等係根據電解處理時間（通電量）而變動。即至一疋時間為止峰值強度增;咸，若超過12〇分鐘則有減少之趨勢。Aggregates are immediately produced and precipitate as time passes. S Example 5 The relationship between the electrolytic treatment and the light absorption spectrum was investigated. In the same manner as in the third embodiment, the psi was electrolytically treated, and before the start of the electrolytic treatment, the electrolysis treatment was started at 5, 1, 2, 3, 3, 45, 6, 〇, 9 〇, 12, °, 150, 180, 210. After 240, 380, and 440 minutes, the sample was sampled, and the light absorption spectrum was measured by a self-made X-ray knife photometer (manufactured by Toray Industries, Ltd.: U-3500). Further, since the measurement is high because the light absorbance is high, the measurement is carried out by diluting the sample several thousand times. The results are shown in Figure 6. The spider PSI originally had light absorption in the vicinity of 5·9 to 6” eV and in the vicinity of 41 to 45 eV, but these were varied depending on the electrolysis treatment time (amount of energization). That is, the peak intensity increases until one hour; salty, if it exceeds 12 minutes, there is a tendency to decrease.

實施例6 調查作為凝集劑，使用在實施例1中使用之聚氯化鋁10 mL之情況時，電解處理時間與凝集效果之關係。電解裝置係使用與實施例1同樣者。電解處理條件如下所示。施加電壓電流值水溫 8 V以下Example 6 The relationship between the electrolytic treatment time and the agglutination effect in the case where 10 mL of the polyaluminum chloride used in Example 1 was used as the aggregating agent was examined. The electrolytic device was the same as in the first embodiment. The electrolytic treatment conditions are as follows. Applied voltage Current value Water temperature 8 V or less

30 mA(定電流控制） 25〇C 146278.doc -20. 201036921 處理時間 30分鐘、6〇分鐘、9〇分鐘及18〇分鐘預先於試管添加2.5 mL純水與〇. 1 mL球蛋白溶液（濃度 2〇〇 μΜ)’再分別添加丨紅如上所得之作為活性化金^ • 二集劑之活性化pAC，充分地攪拌。攪拌後立即以肉眼： • ^ 2、3、4、5及20小時後在試管内所生成之沉 :。將結果顯示於圖7。在圖7中’於照片之右側顯示電解 1夺間，在照片中，從左開始顯示攪拌後立即、靜置 ❹ 3、4、5及2〇小時後之結果。從圖7可知，㈣分鐘解處理者，在靜置2小時後沉澱大量生成，但經30分鐘處理者、及90分鐘處理者、經18〇分鐘處理者靜置2小時後亦雖有生成沉澱，但較經60分鐘處理者生成沉殿更慢。實施例7 —作為凝集劑，使用與在實施例4中使用者相同之聚 I > 1线系凝集劑（PSI)10 mL之情況時，電解處理時間 -凝集效果之關係。電解裝置係使用與實施例^樣者。 Q 電解處理條件如下所示。施加電壓 5V以下电/瓜值 30 mA(定電流控制）水溫處理相30分鐘、6〇分鐘、m分鐘及440分鐘 20:先二試管添加2.5此純水與。」mL球蛋白溶液(濃度 μ ，再分別添加1 mL如上所得之作為凝集削之活一充分嶋。再者，與未二處理相“進行試驗料比較。《转觀察㈣後立 146278.doc -21 - 201036921 即、靜置1、2、3、4、5及20小時後在試管内所生成之沉澱。將結果顯示於圖8。在圖8中’於照片之右側顯示電解处寺間，在照片中，從左開始顯示攪拌後立即、靜置 4 5及20小時後之結果。從圖8可知無關電解處理時間’凝集劑混合後立即生成沉澱，並隨著沉澱增加。 ’ 實施例8 使用與實施例i同樣之裝置，以6〇 mA電解處理“―聚南海㈣株式會社製，1G〜11%)，獲得料活性化至瓜凝集劑之活性化PAC。處理時間設為15、30、90、 ::分鐘。通電量分別為5、1〇、29及59庫侖〜。其 =:::一獲得之活一一之一離Γ捨睾主水溶〉夜。靜置20分鐘後，以2,5〇〇啊離心分沉搬，藉由雷m noc之皿度“所獲得之稽由電子天平測定乾燥重量。未進行電 pac亦同樣進行試驗（处理之之情況之重量設為卜求得虚使^ /^^通電量為0 之活性化PAC之*解處理所獲得圖。將該曲線圖：搬之乾燥重量之比’製作曲線軸為乾#重^“、、、圖9。在圖9中，横轴為通電量，縱乾各重里比。從圖9可知，之乾燥重量相較於電解處理前上升脚:Π，沉激通電量設為60庫命㈣，發現操作中，由於係採「凝集.分離」之：二實，量智Η 4 e 」保作故重要的是大、生長引起固液分離。 146278.doc 201036921 實施例9 除將聚二氧化矽鐵系凝集劑（南海化學工業株式會社製，PSI-〇25)稀釋成1〇/3倍，使用其6 〇 ‘，另使用4 6 mL作為球蛋白溶液4 3 μΜ者以外，與實施例8同樣地進行電解處理、且進行試驗。將結果顯示於圖10。從圖10可知，使用PSI之，晴況’相較於未實施電解處理之情況，進行電解處理者可使乾燥重量上升至J 〇倍以上。又，沉殺之 ❹乾燥重ΐ比在通電量為50庫侖/g時’可獲得最大值，施以該通電量以上之通電效果亦不會上升。實施例10 使用與貫施例8同樣之裝置，以60 mA電解處理在實施例 8中使用之6.0 mL之聚氯化鋁，獲得作為活性化金屬鹽凝集劑之活性化PAC(直流電解處理）。又，使用同樣之裝置，實施根據正弦波（交流、2〇、60及600 Hz)之交流電解處理（時間：90分鐘、通電量：54庫侖/g)。取所獲得之活〇性化PAC I·0 mL，與實施例8同樣地進行試驗。測定將未進行電解處理之乾燥重量設為丨之情況之乾燥重量，結果發現，相對於直流電解之大約為55，交流電解處理之情況均大約為】。即以商用頻率之6〇 Hz之交流進行電解處理，PAC之凝集性能亦不會提高，此在2〇 Hz〜6〇() Hz之範圍内亦不會改變。實施例11 使用與實施例9同樣之裝置，以6〇爪入電解處理實施例9 中使用之6.0 mL之PSI，獲得作為活性化金屬鹽凝集劑之 146278.doc -23· 201036921 活性化PAC(直流電解處理）。又，使用同樣之裝置，實施根據正弦波（交流、20、60及600 Hz)之交流電解處理（時間：90分鐘、通電量：54庫侖/g)。取所獲得之活性化PSI 1.0 mL，與實施例9同樣地進行試驗。測定將未進行電解處理之乾燥重量設為1之情況之乾燥重量，結果，相對於直流電解之大約為9.5，交流電解處理之情況均大約為1。即以商用頻率之60 Hz之交流進行電解處理，PSI之凝集性能亦不會提高，此在20 Hz〜600 Hz之範圍内亦不會改變。實施例12 由於已了解進行直流電解處理時，凝集劑之凝集性能提高，故可推定該效果係由任一方之電極反應而產生。因此，進行以過濾件隔離電解槽之實驗。使用與實施例1同樣之裝置，在陽極與陰極之間，配置浸透膜，將陽極與陰極隔離。藉此，電氣上而言陽極側之 PAC(PSI)與陰極側之PAC呈導通狀態，但成為陽極側之 PAC(PSI)與陰極側之PAC不易混合之條件。以100 mA電解處理10分鐘及30分鐘，並抽樣陽極側及陰極側之PAC，_ 實施例8同樣地乾燥並測定乾燥重量，比較未進行電解處理之情況者。將結果顯示於表2中。將使用PAC之情況之結果顯示於以下之表2，並將使用 PSI之情況之結果顯示於表3中。 146278.doc -24· 201036921 表2 電解處理時間凝集體之乾燥重量比 10分 30分陽極側PAC 0.86 3.13 陰極側 0.77 0.78 從表2可知，陽極側之凝集劑凝集性能提高，但陰極側之凝集劑其凝集性能完全沒有提高。其次，就PSI亦同樣地進行試驗。電解處理之條件除配置浸透膜以外與實施例9相同，以30分鐘及60分鐘之電解處理時間實施。將結果顯示於以下之表3中。表3 電解處理時間凝集體之乾燥重量比 30分 60分陽極側PSI 18 18.3 陰極側 1.67 0.67 從表3可知，陽極側之凝集劑凝集性能提高，但陰極側之凝集劑其凝集性能完全沒有提高。30 mA (constant current control) 25〇C 146278.doc -20. 201036921 Treatment time 30 minutes, 6 minutes, 9 minutes and 18 minutes. Add 2.5 mL of pure water and 〇. 1 mL of globulin solution to the test tube. The concentration of 2 〇〇μΜ)' was further added to the activated pCO obtained as the activated gold as the above-mentioned two-concentration agent, and the mixture was sufficiently stirred. Immediately after mixing, the naked eye: • ^ 2, 3, 4, 5, and 20 hours later in the test tube. The results are shown in Figure 7. In Fig. 7, 'electrolysis 1 is shown on the right side of the photograph, and in the photograph, the result immediately after the stirring, after standing for 3, 4, 5, and 2 hours is displayed from the left. As can be seen from Fig. 7, in the (four) minute solution, a large amount of precipitate was formed after standing for 2 hours, but after 30 minutes of treatment, and 90 minutes of treatment, after 18 minutes of treatment, the precipitate was formed even after standing for 2 hours. However, it is slower to generate a sinking hall than a 60-minute processor. Example 7 - As a coagulant, the relationship between the electrolysis treatment time and the agglutination effect was obtained when 10 mL of the same poly->1 line system aggregating agent (PSI) as in Example 4 was used. The electrolysis apparatus is used in the same manner as in the examples. Q Electrolytic treatment conditions are as follows. Applied voltage 5V or less Electric / melon value 30 mA (constant current control) Water temperature Treatment phase 30 minutes, 6 minutes, m minutes and 440 minutes 20: Add 2.5 pure water with the first two tubes. "mL globulin solution (concentration μ, then add 1 mL as above to obtain a sufficient amount of agglutination for the agglutination. Further, compare with the non-treated phase" to compare the test materials. "Turn observation (4) after standing 146278.doc - 21 - 201036921 That is, the precipitate formed in the test tube after standing 1, 2, 3, 4, 5 and 20 hours. The result is shown in Fig. 8. In Fig. 8, the electrolysis temple is shown on the right side of the photograph. In the photograph, the results immediately after stirring and after standing for 4 5 and 20 hours are shown from the left. It can be seen from Fig. 8 that irrespective of the electrolytic treatment time, the precipitate is formed immediately after the aggregating agent is mixed, and increases with the precipitation. In the same manner as in the example i, an "activated PAC" which was activated to a melon aggregating agent was obtained by electrolytically treating "1 to 11%" manufactured by "Poly Nanhai (4) Co., Ltd.) at 6 mA. The processing time is set to 15, 30, 90, :: minutes. The power consumption is 5, 1 〇, 29 and 59 coulombs ~. Its =::: One of the ones that got the life one by one. After standing for 20 minutes, the mixture was centrifuged at 2,5 〇〇, and the dry weight was determined by the electronic balance obtained by Ray Noc. The same test was carried out without electric pac (treatment The weight of the situation is set to the figure obtained by the solution of the activated PAC with the energization amount of 0. The graph: the ratio of the dry weight of the transfer to the curve of the production curve is dry #重^ ",, and Fig. 9. In Fig. 9, the horizontal axis is the amount of energization, and the weight ratio is vertical and dry. As can be seen from Fig. 9, the dry weight is higher than that before the electrolytic treatment: Π, the amount of the energization is set to 60. Kushen (4), found that in the operation, because of the "aggregation. Separation": two real, the quantity of wisdom 4 e "guarantee is important, large, growth caused by solid-liquid separation. 146278.doc 201036921 Example 9 The polyferric oxide iron-based aggregating agent (PSI-〇25, manufactured by Nankai Chemical Industry Co., Ltd.) was diluted to 1〇/3 times, and 6 〇' was used, and 4 6 mL was used as the globulin solution 4 3 μΜ. The electrolytic treatment was carried out in the same manner as in Example 8 and the test was carried out. The results are shown in Fig. 10. When PSI is used, the degree of drying can be increased to more than J 〇 times compared with the case where electrolysis is not performed. Further, the dry weight of the smash is 50 coulomb/g. The maximum value was obtained, and the energization effect of the energization amount or more was not increased. Example 10 Using the same apparatus as in Example 8, the 6.0 mL polymerization used in Example 8 was electrolytically treated at 60 mA. Aluminum chloride, activated PAC (DC electrolysis treatment) as an activated metal salt aggregating agent. Further, AC electrolysis treatment according to sine waves (AC, 2〇, 60, and 600 Hz) is performed using the same apparatus (time) : 90 minutes, energization amount: 54 coulombs/g). The obtained active PAC I·0 mL was taken and tested in the same manner as in Example 8. The measurement was carried out by setting the dry weight without electrolytic treatment to 丨. The dry weight was found to be about 55 with respect to DC electrolysis, and the case of AC electrolysis treatment was about 】. That is, electrolysis treatment was carried out at a commercial frequency of 6 Hz AC, and the agglutination performance of PAC was not improved. At 2〇Hz The range of ～6 〇() Hz does not change. Example 11 Using the same apparatus as in Example 9, 6 mL of PSI was used to electrolytically treat 6.0 mL of PSI used in Example 9 to obtain an activated metal salt. Agglomerating agent 146278.doc -23· 201036921 Activated PAC (DC electrolysis treatment). Further, using the same device, AC electrolysis treatment according to sine wave (AC, 20, 60 and 600 Hz) was carried out (time: 90 minutes, The amount of electricity was 54 coulombs/g. The obtained activated PSI (1.0 mL) was taken and tested in the same manner as in Example 9. The dry weight in the case where the dry weight which was not subjected to the electrolytic treatment was set to 1 was measured, and as a result, it was about 9.5 with respect to the direct current electrolysis, and was about 1 in the case of the alternating current electrolysis treatment. That is, the electrolytic treatment is carried out at a commercial frequency of 60 Hz, and the agglutination performance of the PSI is not improved, which does not change in the range of 20 Hz to 600 Hz. [Example 12] Since it has been known that the aggregating performance of the aggregating agent is improved when the direct current electrolytic treatment is performed, it is estimated that the effect is produced by the reaction of either electrode. Therefore, an experiment of isolating the electrolytic cell with a filter member was carried out. Using the same apparatus as in Example 1, an impregnation membrane was disposed between the anode and the cathode to isolate the anode from the cathode. Thereby, the PAC (PSI) on the anode side and the PAC on the cathode side are electrically connected to each other, but the PAC (PSI) on the anode side and the PAC on the cathode side are not easily mixed. The mixture was subjected to electrolytic treatment at 100 mA for 10 minutes and 30 minutes, and the PAC on the anode side and the cathode side was sampled, and Example 8 was dried in the same manner, and the dry weight was measured, and the case where no electrolytic treatment was performed was compared. The results are shown in Table 2. The results of the case where the PAC was used are shown in Table 2 below, and the results of the case of using the PSI are shown in Table 3. 146278.doc -24· 201036921 Table 2 Drying weight ratio of electrolytic treatment time aggregates 10 minutes 30 minutes anode side PAC 0.86 3.13 cathode side 0.77 0.78 It can be seen from Table 2 that the agglutination performance of the aggregating agent on the anode side is improved, but the agglutination on the cathode side The agglutination properties of the agent were not improved at all. Secondly, the PSI was also tested in the same way. The conditions of the electrolytic treatment were carried out in the same manner as in Example 9 except that the impregnation membrane was placed, and the electrolytic treatment time was 30 minutes and 60 minutes. The results are shown in Table 3 below. Table 3 Drying weight ratio of electrolytic treatment time aggregates 30 minutes 60 minutes anode side PSI 18 18.3 cathode side 1.67 0.67 From Table 3, the agglutination performance of the aggregating agent on the anode side is improved, but the agglutination performance of the aggregating agent on the cathode side is not improved at all. .

實施例13 使用與實施例1同樣之裝置，以60 mA電解處理實施例8 中使用之11 mL聚氯化鋁（南海化學株式會社製、 10〜11%)，獲得作為活性化金屬鹽凝集劑之活性化PAC。處理時間設為5、15、30、60、180分鐘。通電量分別為 2、5、10、20、及59庫侖/g。其次，在試管中，將所獲得之1.0 mL活性化PAC，與2·6 mL之7.7 μΜ濃度之球蛋白溶液混合。靜置20小時後，以2,500 rpm離心分離，並測定上 146278.doc -25- 201036921 月液之光及收光谱。將結果顯示於圖Η。又，將沉趨以 110 C之溫度乾燥，並利用電子天平測定乾燥重量。針對未進行電解處理之PAC亦同樣地進行試驗（該情況之通電量為〇)。將通電量為〇之情況之重量設為丨，求得與使用藉由〇 4解處理所獲得之活性化PAC之情況的沉澱之乾燥重量之比，製作顯示與3.9 eV之吸光度之對比之曲線圖。將該曲線圖顯示於圖12。如圖11所示，將PAC進行電解處理之情況，在圖11中，橫軸顯示能量（eV)，縱軸為吸光度。由於測定之裝置之測 j界限為吸光度3.5，故吸光度為3.5以上之測定資料無可罪度’在圖Π中，3 ·5係以上限而表示。又，從圖12可知，在本實施例中，在49以及39 ^出現光吸收帶，其吸光度隨著通電量之增加而增加。在圖U 中，橫軸顯示3·9 eV之吸光度，縱軸為乾燥重量比。從圖 12可知’若3.9 eV之吸光度增加，則乾燥重量比增加，因此’凝集效率提高。實施例14Example 13 11 mL of polyaluminum chloride (manufactured by Nankai Chemical Co., Ltd., 10 to 11%) used in Example 8 was electrolytically treated at 60 mA in the same manner as in Example 1 to obtain an activated metal salt aggregating agent. Activated PAC. The processing time is set to 5, 15, 30, 60, and 180 minutes. The power consumption is 2, 5, 10, 20, and 59 coulombs/g, respectively. Next, in the test tube, 1.0 mL of the activated PAC obtained was mixed with 2. 6 mL of a 7.7 μL concentration of the globulin solution. After standing for 20 hours, it was centrifuged at 2,500 rpm, and the light and the spectrum of the liquid of 146278.doc -25-201036921 were measured. The results are shown in Figure Η. Further, the sinking was dried at a temperature of 110 C, and the dry weight was measured using an electronic balance. The test was also carried out in the same manner for the PAC which was not subjected to electrolytic treatment (in this case, the amount of energization was 〇). The weight of the case where the amount of electricity was 〇 was set to 丨, and the ratio of the dry weight of the precipitate in the case of using the activated PAC obtained by the treatment of 〇4 was determined, and a curve showing the contrast with the absorbance of 3.9 eV was produced. Figure. This graph is shown in Fig. 12. As shown in Fig. 11, in the case where the PAC is subjected to electrolytic treatment, in Fig. 11, the horizontal axis shows energy (eV) and the vertical axis shows absorbance. Since the measurement j of the measuring device is the absorbance of 3.5, the measurement data having an absorbance of 3.5 or more is not guilty. In the figure, the 3·5 system is represented by the upper limit. Further, as is apparent from Fig. 12, in the present embodiment, the light absorbing bands appear at 49 and 39, and the absorbance thereof increases as the amount of energization increases. In Figure U, the horizontal axis shows the absorbance of 3·9 eV and the vertical axis shows the dry weight ratio. As is apparent from Fig. 12, if the absorbance at 3.9 eV is increased, the dry weight ratio is increased, so that the 'aggregation efficiency is improved. Example 14

就食用肉中心综合廢水篩網池排水（山口縣宇部市。pH 大約6_9)，使用本發明之活性金屬鹽凝集劑，實施水質^ 淨化。使用與實施例1同樣之電解裝置，以下产 a卜迷之條件電解處理聚氯化鋁（與實施例8中使用者相同者），獲得、、舌性化 PAC。又1In the meat center integrated wastewater screen pool drainage (Ube City, Yamaguchi Prefecture, pH about 6_9), the water metal purification is carried out using the active metal salt aggregating agent of the present invention. Using the same electrolysis apparatus as in Example 1, the polyaluminum chloride (the same as the user of Example 8) was electrolytically treated under the following conditions to obtain and ligating PAC. Another 1

施加電壓 7 V 146278.doc •26· 201036921 電流值水溫 60 mA(定電流控制）Applied voltage 7 V 146278.doc •26· 201036921 Current value Water temperature 60 mA (constant current control)

20°C 處理時間 60分鐘預先在試管中將用於濃度調整之85卟純水添加至2.6 L食用肉中心综合廢水網篩池排水中，再添加1 $ 0如上斤得之作為活性化金屬鹽凝集劑之活性化PAC，充分授拌。〇將°式s内所生成之沉澱，於攪拌後立即、靜置3 0分鐘、 1.5小時、3小時及9小時後，以肉眼觀察。 ^又，以下述之電解處理條件，電解處理將聚二氧化矽鐵系凝劑（南海化學工業株式會社製，psi_〇25)稀釋成倍者，獲得活性化PAC。20 ° C treatment time 60 minutes, previously added 85 卟 pure water for concentration adjustment in the test tube to the 2.6 L edible meat center integrated wastewater net sieve pool drainage, and then add 1 $ 0 as the above-mentioned jin as the activated metal salt The agglutinating agent is activated by PAC and fully mixed.沉淀 The precipitate formed in the formula s was observed with the naked eye immediately after stirring, after standing for 30 minutes, 1.5 hours, 3 hours, and 9 hours. Further, the polyphosphorus iron chelating agent (manufactured by Nankai Chemical Industry Co., Ltd., psi_〇25) was diluted by the electrolytic treatment under the following electrolytic treatment conditions to obtain an activated PAC.

施加電壓 4 V 電流值 100 mA(定電流控制）水溫 20。(： ❹ 處理時間 3 0分鐘預先在試管中將用於濃度調整之7〇卟純水添加至26 • 食用肉中心綜合廢水篩網池排水中，再添加3〇叫如上所得之作為活性化金屬鹽凝集劑之活性化pAC，充分攪 •拌。將於試管内所生成之沉澱，於攪拌後立即、靜置3〇分知、1.5小時、3小時及9小時後’以肉眼觀察。將結果顯示於圖13。在圖13中，左側為使用pac之系，PAC之列係使用作為較之未進行電解處理之PAC之實驗，e_pAc之列係使用 J46278.doc -27- 201036921 電解處理之PAC之實驗，右側係使用PSI之系，psi之列係使用作為比較之未進行電解處理之psI之實驗，e_psi之列係使用電解處理之PSI之實驗。從圖〗3可知，使用電解處理之PAC或PSI時，相較於未進行電解處理者，沉澱量較多。實施例15 在實施例14之實驗中，藉由肉眼觀察靜置9小時之試管結束後’#由離心分離回收上清液，並測定光透射光譜。將結果顯示於圖14。從圖14可知，pAC及psi任一者均為經電解處理者上清液之透射率高。其顯示廢水所含有之物^ 可藉由經電解處理之凝集劑有效地去除。實施例16 就公共廢水最初沉澱池排水（山口縣宇部市、p h值大約 6.5〜7_D，使用實施例14中所獲得之活性化pAc及活性化 PSI，進行與實施例3相同之處理，靜置9小時後，測定其上清液之光透射光譜。將結果顯示於圖15。從圖啊知，、 PAC及PSI任一者均為經電解處理去一听地里考上清液之透射率高。其顯示廢水所含有之物質可藉由經電觫、电解處理之政集劑有效地去除。【圖式簡單說明】Applied voltage 4 V Current value 100 mA (constant current control) Water temperature 20. (: ❹ The treatment time is 30 minutes, and the 7 〇卟 pure water used for concentration adjustment is added to the tube in advance in the test tube. • The wastewater is collected in the integrated wastewater screen pool of the meat center, and 3 〇 is added as the activated metal. The salt agglutinating agent is activated by pAC, and the mixture is stirred thoroughly. The precipitate formed in the test tube is immediately after being stirred for 3 minutes, and after 1.5 hours, 3 hours, and 9 hours, it is observed by the naked eye. Shown in Figure 13. In Figure 13, the left side is the system using pac, the PAC column is used as the experiment compared to the PAC which has not been subjected to electrolytic treatment, and the e_pAc column is the electrolytically treated PAC using J46278.doc -27- 201036921 In the experiment, the PSI system was used on the right side, the psi column was used as the comparative psI experiment without electrolytic treatment, and the e_psi column was the experiment using the electrolytically treated PSI. From Fig. 3, the electrolytically treated PAC was used. In the case of PSI, the amount of precipitation was larger than that in the case where electrolysis was not performed. Example 15 In the experiment of Example 14, the supernatant was collected by centrifugation after the end of the test tube which was left to stand for 9 hours by the naked eye. And measuring Transmission spectrum. The results are shown in Fig. 14. As can be seen from Fig. 14, both of pAC and psi have high transmittance of the supernatant of the electrolytically treated liquid, which indicates that the contents of the wastewater can be treated by electrolysis. The aggregating agent was effectively removed. Example 16 The initial sedimentation tank drainage of the public waste water (Ube City, Yamaguchi Prefecture, ph value of about 6.5 to 7_D, using the activated pAc and activated PSI obtained in Example 14 was carried out, and Example 3 was carried out. The same treatment, after standing for 9 hours, the light transmission spectrum of the supernatant was measured. The results are shown in Fig. 15. From the figure, any of PAC and PSI are treated by electrolysis. The supernatant has a high transmittance, which indicates that the substance contained in the wastewater can be effectively removed by the electrolysis and electrolysis treatment. [Simplified illustration]

圖1係顯示隨著時間之經過之球蛋白之凝集狀態的照片、之照片； ’利用經活性化處理之PAC 及用於比較之未處理之PACFig. 1 is a photograph showing a state of aggregation of globulins over time, and photographs thereof; 'Using activated PAC and untreated PAC for comparison

圖2係顯示隨著時間之經過，利用經活性化處理之PAC 146278.doc -28- 201036921 蛋白之滅集狀態的照片、及用於比較之未處理之PAC 之照片；圖3係顯示PAC之活性化電解處理之處理時間與光吸收光譜之變化的圖（處理時電流值為30 mA); 圖4係將光吸收光譜之初期光吸收光譜減算，並明確顯不源自電解處理之變化之增加成份的圖（處理時電流值為 30 mA)； K 5係用於顯示進行活性化處理之PSI之情況與未進行活〇性化處理之PSI兩者之不同的照片；圖6係顯示PSI之活性化處理時間所造成之光吸收光譜之變化的圖（χΐ/6〇〇〇); 圖7係顯示PAC之活性化處理時間與凝集性能之關係之照片；圖係,4示PSI之活性化處理時間與凝集性能之關係之照片；圖9係顯示通電量盘齡條產_ 〜％里/、钇备重I比之關係之曲線圖； Ο 圖10係顯示通電量盘教焯逢·旦y %里，、乾琛重里比之關係之曲線圖；圖11係顯示通電量與吸光度之關係之曲線圖； • _顯示通電量與乾燥重量比之關係之曲線圖；圖【3係顯示以凝集劑處理食用肉中心综合廢水之實驗之結果之照片；圖14係顯示以凝集劍虑：王里人士 a 朱剐返理食用肉中心綜合廢水之實驗的上清液之光透射光譜之測定結果；及圖15係顯示以凝集劑盧理八#由，π 剧爽理公共廢水最初沉澱池排水之實驗的上清液之光透射光譜之測定結果。 146278.doc •29·Figure 2 is a photograph showing the state of extinction of the activated PAC 146278.doc -28-201036921 protein over time, and a photograph of the untreated PAC for comparison; Figure 3 shows the PAC Diagram of the change of treatment time and light absorption spectrum of activated electrolysis treatment (current value of treatment is 30 mA); Figure 4 is the calculation of the initial light absorption spectrum of the light absorption spectrum, and clearly shows that it does not originate from the change of electrolytic treatment. A graph of increasing the composition (current value of 30 mA during processing); K 5 is used to display a photograph of the PSI for the activation treatment and the PSI for the non-activated treatment; Figure 6 shows the PSI Fig. 7 is a photograph showing the relationship between the activation treatment time of PAC and the agglutination performance; Figure 4 shows the activity of PSI activity. A photograph showing the relationship between the treatment time and the agglutination performance; Fig. 9 is a graph showing the relationship between the energization amount and the age of the product, and the ratio of the weight to the ratio of the weight I; In the y%, the relationship between the dry and the heavy Figure 11 is a graph showing the relationship between the amount of electricity and the absorbance; • _ shows the relationship between the amount of electricity and the dry weight ratio; Figure 3 shows the results of the experiment on treating the integrated wastewater from the meat center with aggregating agent Photograph; Figure 14 shows the results of the light transmission spectrum of the supernatant of the experiment in which the Wang Li person a Zhu Xi returned to the meat center integrated wastewater; and Figure 15 shows the agglutinating agent Lu Li #由,π The results of the measurement of the light transmission spectrum of the supernatant of the experiment of the initial sedimentation tank drainage of public wastewater. 146278.doc •29·

Claims

201036921 VII. Patent application scope: 1. - An active metal salt is condensed (4). The metal salt aggregating agent or an aqueous solution containing the metal salt aggregating agent is electrolytically treated. 2. An active metal salt aggregating agent as claimed, wherein the metal salt aggregating agent is a polymeric metal salt aggregating agent. The active metal ruthenium aggregating agent of claim 2, wherein the metal salt aggregating agent is a polyaluminum chloride-based aggregating agent. 4. Shi Ming seeking items! An active metal salt aggregating agent having a light absorption band at 4.8 to $5^ and 3.8 to 4.2 eV. 5. The active metal ruthenium aggregating agent of claim 2, wherein the metal salt aggregating agent is a polyferric ruthenium iron aggregating agent. 6. The active metal salt aggregating agent of claim 5, wherein the absorbance of the light absorption band of 59 to 61 is lower than that before the electrolytic treatment. 7. An active metal salt aggregating agent as claimed, wherein the electrolytic treatment is a direct electrolytic treatment. 8. A method for producing an active metal salt aggregating agent, characterized in that a metal salt aggregating agent or an aqueous solution containing the metal salt aggregating agent is present in a container having two electrodes which are electrodes of both the anode and the cathode, and Power is applied between the two electrodes. 9. The method for producing an active metal salt aggregating agent according to claim 8, which comprises the step of charging the container on the anode side and the cathode side by a diaphragm, and recovering the aggregating agent on the anode side. 10. The method for producing an active metal salt aggregating agent according to claim 8, wherein the amount of electricity is 5 to 60 liters/g. A method of producing an active metal salt aggregating agent according to claim 8, wherein the power generation system is performed by applying a direct current voltage. A method for purifying water, which comprises the step of bringing the active metal salt aggregating agent of claim 1 into contact with water to be treated, and purifying the water to be treated. 146278.doc