200938491 六、發明說明： 【韻^明所屬貝域^ 發明領域 [0001] 本發明係有關於含有過氧化氫之水之過氧化氫 5 除去方法及其裝置、臭氧水製造方法及其裝置、以及洗淨 方法及其裝置。 本申請案係依2007年12月26向日本專利廳提申之曰本 專利申請案2007-333451號主張優先權，於此沿用其内容。 © 【】 10 發明背景 [0002] 如第5圖所示，習知用於半導體產業之石夕晶圓之 _ 洗淨等之所謂超純水(二次純水)以由前處理系統1 〇、一次純 水系統20'二次純水系統(次系統)4〇構成之超純水製造装裏 P· 210，處理原水(工業用水、都市用水、井水等）來製造。 15 [〇〇〇3]第5圖之各系統之功用如下。前處理系統i〇以廣 水槽12、凝結沉澱裝置14、過濾裝置16、過濾水槽18構成。 ❹ 前處理系統進行原水槽12之原水中之懸浮物質或膠質物質 之去除。一次純水系統2〇由離子交換裝置22、紫外線照射 裝置24、精密過濾裝置26、逆滲透(R〇)膜裝置28、除氣装 2〇置30構成。在-次純水系統2〇中，進行業經以前處理系統 1〇去除懸浮物質之原水之離子或有機成份之去除而獲得 一次純水。 [0004]次系統40為製造超純水之系統。次系统以〆农 純水槽42、熱交換器44、紫外線氧化裝置46、非再生贺雜 200938491 子交換裝置48、最終過濾、器(UF膜)裝置5〇構成。非再生型 離子父換裝置48填充有含有陰離子交換劑之離子交換劑。 次系統40係更提高以-次純水系統2〇獲得之一次純水之純 度，製造超純水之步驟。將以一次純水系統2〇獲得之一次 5純水儲存於一次純水槽42。以熱交換器44將一次純水槽42 之一次純水調整至預定溫度。接著，以紫外線氧化裝置46 照射紫外線，將純水中之TOC(總有機碳)分解至有機酸、甚 至是二氧化碳。有機酸、二氧化碳、以非再生型離子交換 裝置48之陰離子交換劑去除。再者，以UF膜裝置5〇去除微 10 粒子，而製造超純水。超純水一面在次系統4〇内循環，一 面維持純度。另一方面，超純水之一部份供給至各使用點 250、252、254。在各使用點，將超純水直接用於晶圓等之 洗淨’或者將臭氧溶解於超純水後，用於洗淨。 [0005]如上述，製造超純水時，以紫外線氧化裝置分解 15 純水中之T0C成份’已知以此紫外線照射，產生10〜30ppb 左右之過氧化氫。截至目前為止，純水中之過氧化氫之除 去方法、除去裝置已揭示組合了氧化性物質分解裝置與膜 式除氣裝置者(例如專利文獻1)、以從非再生型離子交換裝 置至膜脫氣裝置之順序通水者(如專利文獻2)、接觸金屬離 20 子型陽離子交換樹脂之方法(例如專利文獻3)、接觸負載有 鈀之觸媒樹脂之裝置(例如專利文獻4)、接觸還原性樹脂之 方法(例如專利文獻5)、設置有觸媒式氧化性物質分解裝置 者（例如專利文獻6)、接觸負栽有亞硫酸離子之陰離子交換 樹脂之方法(例如專利文獻7)等。如上述，為去除純水中之 200938491 5200938491 VI. Description of the invention: [Yunming ^ Ming belongs to the field] FIELD OF THE INVENTION [0001] The present invention relates to a method and apparatus for removing hydrogen peroxide 5 containing water of hydrogen peroxide, a method and apparatus for producing ozone water, and Washing method and device thereof. The present application claims priority to Japanese Patent Application No. 2007-333451, filed on Dec. © [Technical Background] [0002] As shown in Fig. 5, the so-called ultrapure water (secondary pure water) used in the semiconductor industry for the cleaning of the semiconductor wafer is used in the semiconductor processing industry. P. 210, a pure water system 20' secondary pure water system (sub-system) 4 〇 ultra-pure water manufacturing equipment, which is manufactured by processing raw water (industrial water, urban water, well water, etc.). 15 [〇〇〇3] The functions of each system in Figure 5 are as follows. The pretreatment system i is composed of a wide water tank 12, a condensation sedimentation device 14, a filtration device 16, and a filtration water tank 18. ❹ The pretreatment system removes suspended matter or colloidal material from the raw water of the raw water tank 12. The primary pure water system 2 is composed of an ion exchange unit 22, an ultraviolet irradiation unit 24, a precision filtration unit 26, a reverse osmosis (R〇) membrane unit 28, and a degassing unit. In the secondary pure water system, the pure water is obtained by removing the ions or organic components of the raw water from which the suspended matter is removed by the prior treatment system. Subsystem 40 is a system for producing ultrapure water. The secondary system is composed of a sapphire pure water tank 42, a heat exchanger 44, an ultraviolet ray oxidizing device 46, a non-regenerating heterogeneous 200938491 sub-exchange device 48, and a final filter (UF membrane) device. The non-regeneration type ion parent changing device 48 is filled with an ion exchanger containing an anion exchanger. The secondary system 40 further increases the purity of the primary pure water obtained by the secondary pure water system 2, and the step of producing ultrapure water. One pure water obtained in one pure water system was stored in a pure water tank 42. The primary pure water of the primary pure water tank 42 is adjusted to a predetermined temperature by the heat exchanger 44. Next, ultraviolet rays are irradiated by the ultraviolet ray oxidizing device 46 to decompose TOC (total organic carbon) in pure water to an organic acid or even carbon dioxide. The organic acid, carbon dioxide, is removed by an anion exchanger of a non-regenerated ion exchange unit 48. Further, ultrafine water was produced by removing the micro 10 particles by the UF membrane device 5 . The ultrapure water circulates within 4 turns of the secondary system to maintain purity on one side. On the other hand, one part of the ultrapure water is supplied to each of the use points 250, 252, 254. At each point of use, ultrapure water is directly used for washing of wafers or the like, or ozone is dissolved in ultrapure water and used for washing. As described above, when ultrapure water is produced, the T0C component in the pure water is decomposed by the ultraviolet oxidizing device. It is known that the ultraviolet ray is irradiated to generate hydrogen peroxide of about 10 to 30 ppb. Up to now, a method and a removal apparatus for removing hydrogen peroxide in pure water have revealed that an oxidizing substance decomposing apparatus and a membrane type degassing apparatus are combined (for example, Patent Document 1), and from a non-regenerating type ion exchange apparatus to a membrane. A sequence of a degasser (such as Patent Document 2), a method of contacting a metal-free cation exchange resin (for example, Patent Document 3), and a device for contacting a catalytic resin loaded with palladium (for example, Patent Document 4) A method of contacting a reducing resin (for example, Patent Document 5), a device equipped with a catalytic oxidizing substance decomposition device (for example, Patent Document 6), and a method of contacting an anion exchange resin loaded with a sulfite ion (for example, Patent Document 7) Wait. As mentioned above, in order to remove pure water 200938491 5
10 1510 15
$氧化氫’使肖_子交換裝置、制是陰離子交換劑去 除之方法。 [0006]又，因純水中之過氧化氫加速臭氧之自分解速 度針對此種問題，揭示使用已減低過氧化氫濃度之超純 水之臭氣水製造方法(專利文獻8)。 [〇〇〇7]然而，當於離子交換裝置排出含有過氧化氫之水 定期間時，有過氧化氫去除能力降低，過氧化氫滲漏許 多至處理水中之問題。 【專利文獻1】日本專利公開公報平11_77〇91號 【專利文獻2】曰本專利公開公報平10—57956號 【專利文獻3】日本專利公開公報平η-277059號 【專利文獻4】曰本專利公開公報平9-192658號 【專利文獻5】日本專利公開公報平Ή%。號 【專利文獻6】曰本專利公開公報2002-210494號 【專利文獻7】日本專利公開公報2〇〇 1_179252號 【專利文獻8】日本專利公報第37342〇7號 C發明内容】 發明概要 用以解決發明之課題 [0008]本發明儀以可長期以離子交換裝置有效地從含 有過氧化氫之水去除過氧化氫為課題。 用以解決課題之手段 _9]本發明人發現騎氧化氫之去除能力已降低之 離子交換裝置，於-定期間停止通水時，過氧化氫之去除 20 200938491 能力再度恢復，而可去除水中之過氧化氫，而終至發明本 發明。 [0010]即’本發明之過氧化氫除去方法係使含有過氧化 風之水間歇地通過填充有OH型陰離子交換劑之離子交換 5裝置。在前述方法中，亦可將前述離子交換裝置並列排列 複數個，使前述含有過氧化氫之水交互地通過複數個離子 交換裝置。前述離子交換裝置亦可為〇H型陰離子交換劑之 單床形態。前述OH型陰離子交換劑亦可為強鹼性陰離子交 換劑。The "hydrogen peroxide" is a method for removing the ana-exchange device and the anion exchanger. Further, the rate of self-decomposition of ozone by the hydrogen peroxide in the pure water is directed to such a problem, and a method for producing an odorous water using ultrapure water having a reduced hydrogen peroxide concentration is disclosed (Patent Document 8). [〇〇〇7] However, when the ion exchange device discharges the water containing hydrogen peroxide, the hydrogen peroxide removal ability is lowered, and the hydrogen peroxide leaks to a large extent in the treated water. [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Publication No. Hei 9-192658 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. [Patent Document 6] Japanese Laid-Open Patent Publication No. 2002-210494 [Patent Document 7] Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. SUMMARY OF THE INVENTION [0008] The apparatus of the present invention is capable of efficiently removing hydrogen peroxide from water containing hydrogen peroxide by an ion exchange apparatus for a long period of time. Means for Solving the Problem _9] The inventors have found that an ion exchange device having reduced the ability to remove hydrogen peroxide can remove hydrogen peroxide during the period of stopping the water supply during the period of 20-200938491, and the water can be removed again. Hydrogen peroxide, and finally to the invention. [0010] That is, the hydrogen peroxide removing method of the present invention is such that the water containing peroxidic air is intermittently passed through an ion exchange apparatus 5 filled with an OH type anion exchanger. In the above method, the plurality of ion exchange devices may be arranged in parallel, and the water containing hydrogen peroxide may be alternately passed through a plurality of ion exchange devices. The ion exchange device may also be in the form of a single bed of a 〇H type anion exchanger. The aforementioned OH type anion exchanger may also be a strongly basic anion exchanger.
10 15 20 L叫i i』个f明义旲氧水製造方法係…q 去方法將臭氧溶解於已去除過氧化氫之水者 [0012]本發明之過氧化氫除絲置包含有填充有 陰離子交換狀離子交換裝置、及使含有過氧化氫之水 歇地通過該離子交換裝置之機構。在此裝置中，亦可包 有將前述離子交換裝置並排排列複數個，使前述含有過 化氫之水交互地通職_離子交換裝置的機構。前述彳 子交換裝置村為子錢狀單床形態 OH型陰離子交換劑亦可為強驗性陰離子交換劑。 _3]本發明之臭氧水製造裝置包含有前述過氧化 除去裝置及將臭氧溶解於已去除魏化氫之水之機構。 _4]本發明之洗淨方㈣㈣經以前述過氧化氯 =去除魏化氫之錢淨電子零件或電子零件之製 i裝署*本發明U較置係包含有料過氧化氫 去裝置、料財除過魏氫之水洗淨電子零件或電子10 15 20 L is called ii 』 f f 旲 旲 旲 旲 旲 q q q 去 去 去 去 去 去 去 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 臭氧 [ [ [ [ [ [ [ [ An exchange ion exchange device and a mechanism for allowing water containing hydrogen peroxide to pass through the ion exchange device. In the apparatus, a plurality of the ion exchange apparatuses may be arranged side by side, and the hydrogen-containing water may be alternately operated by the ion exchange apparatus. The scorpion exchange device village is a singular single bed form OH type anion exchanger or a strong anion exchanger. The ozone water producing apparatus of the present invention comprises the above-described peroxide removing apparatus and means for dissolving ozone in the water from which hydrogen sulfide has been removed. _4] The cleaning party of the present invention (4) (4) by the above-mentioned chlorine peroxide = the removal of Weihua hydrogen money net electronic parts or electronic parts manufacturing system * the U-based system contains the material hydrogen peroxide to the device, the material has been removed Wei hydrogen water washes electronic parts or electronics
6 200938491 件之製造器具。 發明效果 [0015]根據本發明之過氧化氫除去方法，可長期以離子 交換裝置效地從含有過氧化氫之水去除過氧化氫 5 圖式簡單說明 [0016] 第1圖係顯示本發明第1實施形態之超純水製造裝置之 流程圖。 Q 第2圖係顯示本發明第2實施形態之超純水製造裝置之 10 流程圖。 第3圖係顯示本發明第3實施形態之超純水製造裝置之 流程圖。 第4圖係顯示本發明第4實施形態之超純水製造裝置之 流程圖。 15 第5圖係習知一般超純水製造裝置之流程圖。 t實方包方式3 〇 用以實施發明之最佳形態 [0018] (第1實施形態） 20 使用第1圖，就本發明過氧化氫除去裝置之第1實施形 態作說明。第1圖係本發明實施形態之超純水製造裝置8之 流程圖。此外，本發明中，「純水」係包含「超純水」者。 [0019]超純水製造裝置8係於第5圖所示之超純水製造 裝置210追加由1個離子交換裝置52、開關閥51、控制裝置 7 200938491 70構成之過氧化氫除去裝置53者，以前處理系制、— 純水系統2〇、次系統40、過氧化氫除去裝置53構成。於^ 系統4 〇與使用點6 G間依序配置關閥51及離子交換裝^ 52。又，次系統40與各使用點62、64連接。 5 [麵]前處理祕1G依序設置原水槽12、凝結沉凝農置 14、過濾、裝置16、過渡水賴。前處理祕10進行原水槽 12之原水中所含之懸浮物質或膠質物質之去除。原水^ 12、凝結沉狀置14、過餘置16、過濾水槽18未特別限 定，可使用既有之裝置。 1〇 [0021]一次純水系統20依序設置離子交換裝置22、紫外 線照射裝置24、精密過濾膜裝置26、RO膜裝置28、除氣裝 置30。離子交換裴置22填充有離子交換劑。離子交換劑之 填充形態未特別限定，為陰離子交換劑或陽離子交換劑之 單床形態或者陰離子交換劑與陽離子交換劑之混合床形態 15 或複床形態等任一形態皆可。 [0022] 紫外線照射裝置24未特別限定，可使用既有之裝 置。例如有除了可照射254nm附近之波長之紫外線，亦可照 射185nm附近之波長之紫外線的紫外線氧化裝置。可強烈照 射185nm附近之波長之紫外線的紫外線氧化裝置在分解以 20 前處理系統獲得之過濾水所含之TOC成份之點為佳。 [0023] 精密過濾膜裝置26未特別限定，可使用既有之裝 置。又，RO膜裝置28未特別限定，可使用既有之裝置。除 1氣裝置30未特別限定，可使用既有之裝置。舉例言之，可 為真空除氣裝置或膜除氣裝置等》 200938491 _4]次㈣4G係更提高以—次純水系㈣獲得之〜 次純水之純度，製造超純水之仏。㈣義依序設置〜 5 ❹ 10 15 ❹ 20 次純水槽42、熱交換器44、料線氧化裝置46、非再生型 離子交換裝448、最终诚_叫裝㈣4可使 水循環。 L』綠魏裝置46只要具有可有效分解-次純 水中之皿成份之能力者，未特觀定，可制既有之裝置。 _6]非再生型離子交換裝置48可使有既有之裝置。 又’於非再生型離子交換裝置48填充有離子交換劑。 交換劑之填充形態未特職定，為陰離子賴劑或陽 交換劑之單床形_者_子域__子緖劑之現 合床形態或複床形態等任—形態皆可，以依—次純水 質或目的之超純水之水質來蚊騎。 广 ，錢冑批要可使域水躲何溫度， 別限定，可使用既有之裝罟。v TTr ^ 可使用既有之裝置。媒襄置5〇未特別限定， [〇〇28]離子交㈣置52只要填充〇地_子交換劑， 填充形態未特別限定。可為如型_衫㈣之單_ 態，亦可為與其他陰離子交換劑之混合床形態，亦可為與 陽離子交換狀混合床形態或者複床形態。惟，從有效去 除過氧化狀觀點，〇_陰料錢綱單床職填充為佳。 [0029]OH型陰離子交換劑可為強驗性陰離子交換劑， 亦可為弱祕陰離子交_。惟，從過氧化氫之去除能力 提高之觀點，以選擇強鹼性交換劑為佳。 9 200938491 [0030]OH型陰離子交換劑之種類未特別限定，可為離 子交換樹脂、離子交換纖維、整塊形多孔質離子交換劑等。 當中，宜使用通用性高之離子交換樹脂。又，離子交換樹 脂之形狀亦未特別限定，可為凝膠形、多孔形或巨孔形。 5 [0031]再者，填充於離子交換裝置52之離子交換劑可為 再生型’亦可為非再生型，當使離子交換劑再生時，因有 污染之可能性，故在設置於使用點6〇前之本實施形態中以 非再生型為佳。又，離子交換裝置52於二次側以具有通風 閥為佳。於停止通水時，滯留於裝置内之水有為離子交換 ❾ 10 劑或離子父換裝置52内壁之溶析物污染之情形，此為排出 開始通水後之污染水之故。 [0032] 本實施形態之過氧化氫除去裝置53以離子交換 裝置52、開關閥51、控制裝置7〇構成。 - [0033] 「使含有過氧化氫之水間歇地通過填充有OH型 15陰離子交換劑之離子交換裝置之機構」係指進行對離子交 換裝置52之通水與通水停止之控制裝置，只要為具有此種 功能者，未特別限定。舉例言之，可為每隔一定期間，進 ❹ 行設置於離子交換裝置52之-次側之開關閥51之開關的控 制裝置70或進行用峨㈣統4〇將超純水輸送至離子交換 20裝置52之泵之啟動及停止的控制裝置。又，開關閥51之開 關及前述泵之啟動及停止可自動進行或手動進行。 [0034] 說明本實施形態之超純水之製造方法及超純水 中之過氧化氫之除去方法。 [0035] 在前處理系統10中，原水槽12接收原水後 ，將原 10 200938491 5 Ο 10 15 20 水依序以沉澱凝結槽14、過濾裝置ι6處理，主要進行膠質 或懸浮物質等之除去，而獲得過濾水。將所獲得之過濾水 貯存於過濾水槽18。在一次純水系統2〇中，將過濾水槽18 之過濾水以離子交換裝置22藉離子交換劑吸附去除離子成 份或者進行交換離子之TOC之去除。 [0036] 接著，以紫外線照射裝置24對過濾水照射紫外 線，進行過濾水之殺菌或將過濾水中之T〇c成份分解至有 機酸、甚至是二氧化碳之㈣。接著，以精密過濾膜裝置 26、RO膜裝置28去除粒子成份或在紫外線照射裴置24生成 之有機酸等分解物等。進-步，將渗透水赠氣裝置3〇去 除溶解氧，而獲得一次純水。 [0037] 在次系統4〇，將以一次純水系統2〇獲得之一次純 水之純度進-步提高而獲得超純水。將以—次线獲得之 -次純水貯存於-次純水槽42。將—次純水以熱交換器44 達預定溫錢’以紫祕氧化裝置46歸紫外線，將水中 之T〇C成份分解至有錢、甚至是二氧化碳之狀態。此外， 在照射紫外線之期間’於水中生成魏化氫。接著，以非 再生型離子交縣置48去雜量之離子絲及以紫外線照 射生成之有機酸或二氧化碳。 [0038] 以UF膜裝置5〇去除微粒子，而獲得超純水。所 得之超純水之—部份直接送至使賴62、64。X，所得之 超，，屯水之，、他部份通過離子交換裝置52，與G时陰離子交 換劑接觸去_氧化氫後，輸送至使㈣6G。其他部份 之超純水送回—次純水槽42，在次系統螺環。從次系統 11 200938491 40進行對離子交換裝置52之通水一定期間後，以控制裝置 70關閉開關閥51，停止通水。停止通水後，經過預定時間， 以控制裝置70開啟開關閥51，再開始通水，而再開始超純 水中之過氧化氫去除。如此，反覆進行對離子交換裝置52 5 之通水及停止。 [0039] 超純水對離子交換裝置52之流量未特別限定，可 依離子交換裝置52之能力決定。舉例言之，相對於陰離子 交換劑之空間速度（SV)以在1〜500L/L-R . h-Ι之範圍設定 為佳’以在10〜100L/L-R _ h-Ι之範圍設定為更佳。此外， 1〇 SV係以相對於離子交換劑之單位體積…幻在丨小時流通之 流量（L)之L/L-R · h-Ι表示。 [0040] 本實施形態之對離子交換裝置52之通水期間未 特別限定，考量超純水中之過氧化氫量或處理量，以在維 持可去除至所期濃度以下之能力之期間内任意設定為佳。 15 又，通水期間可以一定時間設定，亦可在離子交換裝置52 之二次側測量過氧化氫之量，將達—定濃度之時間點設定 作為通水期間之終點。 [0041] 停止對離子交換裝置52之通水之期間未特別限 定，考量超純水之處理量、超純水中之過氧化氫濃度、離 2〇子父換裝置52之規模等，可設定離子交換裝置52之過氧化 氫去除能力恢復之期間。舉例言之，要處理含有15〜3〇ppb 之過氧化氫之超純水，將過氧化氫濃度維持在1〇ppb以下， 以在1小時至24小時之範圍，設定停止通水之期間為佳。此 外以於通水開始後即刻排出滯留於離子交換裝置52内之 12 200938491 污染水後，將業經去除過氧化氣之超純水供給至使用點6〇 為佳。這是由於可防止使用點之污染之故。 [0042] 去除本實卿態之軌化氫叙超純水未特別 限定，以電阻率15ΜΩ . cm以上、就1〇响以下為佳。又， 5超純水之水溫未特.定，以5〜贼為佳，15〜聊為更 佳，20〜25°c尤佳。 ‘ [0043] 根據本實卿態，藉停止對離子交換裝置&之超 純水之通水，可使離子交換袈置52之過氧化氯去除能力恢 復。因此’藉反覆進行對離子交換裝置52之通水及停止， 10 可長期有效地去除超純水中之過氧化氫。 [0044] (第2實施形態） 使用第2圖’就本發明之過氧化氨除去裝置之第2實施 形態作說明。第2圖係第2實施形態之超純水製造裝置1〇〇之 15流程圖。本實施形態係將第1圖所示之第1實施形態之過氧 化氫除去裝置53變更成將離子交換裝置52&、52b並列配置 之過氧化氫除去裝置55者。又，本實施形態之過氧化氫除 去裝置55係將離子交換裝置52a、52b並排配置，於離子交 換裝置52a之一次侧連接開關閥5ia，於離子交換裝置52b之 20 一次侧連接開關閥51b而構成。再者，於開關閥51a、52b連 接控制裝置72。開關閥51a與51b之一次側之流路統合為1個 流路，與次系統40連接。離子交換裝置52a與52b之二次側 流路統合為1個流路後’與使用點61連接。 [0045]本實施形態之「使含有過氧化氫之水交互地通過 13 200938491 複數離子交換裝置之機構」係指交互進行對離子交換裝置 52a、52b之通水及通水停止的控制裝置，只要為具有此功 能者，未特別限定。舉例言之，亦可為每隔一定期間交互 進行設置於離子交換裝置52a、52b之一次側之開關閥5ia、 5 51b之開關的控制裝置72或進行從次系統4〇分別送水至離 子交換裝置52a、52b之泵之啟動及停止的控制裝置。又， 開關閥51a、51b之開關及前述泵之啟動及停止可自動進 行’亦可手動進行。 [0(M6]就本實施形態之超純水之製造方法、超純水中之 10 過氧化氫之除去方法作說明。 [0047] 將以次系統4〇製造之超純水通過離子交換裝置 52a，去除過氧化氫後，供給至使用點61。於離子交換裝置 52a通水一定期間後，以控制裝置72，令開關閥5ib開啟， 對離子父換裝置52b開始通水。此時，以離子交換裝置52b 15處理之水不供給至使用點61而排出。另一方面，繼續以離 子交換裝置52a處理之水對使用點61之供給。經過_定期間 後，停止離子交換裝置52b之排出水，將以離子交換裝置52b 處理之水供給至使用點61。接著，以控制裝置72令開關閥 51a關閉，停止對離子交換裝置52a之通水。如此進行，離 2〇 广 子交換裝置52a之過氧化氫除去切換為離子交換裝置52b之 過氧化氫除去。 [0048] 於離子交換裝置52b通水一定期間後，以控制裝 置72令開關閥51a開啟，開始對離子交換裝置52a之通水。 此時，以離子交換裝置52a處理之水不供給至使用點61而排 200938491 6出 1之二方面’繼續以離子交換裝置现處理之水對使用點 ^於—定期騎束後，停止離子交換裝置52a之排 — 仏離子交換裝置仏處理之水供給至使用點6卜接 5 10 15 ❹ 20 =控制裝置72令開_51b為關閉，停止對離子交換裝 之通水。如此’反覆騎離子交換裝置52a與52b之通 水轉’進行超純水中之過氧化氫之除去，將已去除過氧 化氯之超純水輸送至使用點61。 陶9]離子交換裝置52a、52b可使用與第！實施形態之 離子父換I置52相时。對離子交歸置仏、灿之通水 期間未特職定，考慮超純水巾之過氧化氫量、處理量或 者離子交換裝置52a與52b之過氧化氫去除之恢復期間，可 在可維持將超純水巾之過氧化氫去除至所㈣度以下之能 力之d間内任思設疋。又，通水期間亦可於經過預定期間 後，停止通水，亦可在離子交換裝置52&、52b之二次側測 量過氧化氫之量，在到達一定濃度之時間點停止通水。 [0050]停止對離子交換裝置52a、52b之通水之期間未特 別限定，考慮超純水之處理量、超純水中之過氧化氫濃度、 離子交換裝置52a、52b之規模等，可設定過氧化氫去除能 力恢设之期間。舉例言之，要處理含有15〜3〇ppb之過氧化 鼠之超純水，將過氧化氛濃度維持在1 〇ppb以下，以在1小 時至24小時之範圍，設定為佳。又，在離子交換裝置523與 52b之切換時之通水再開始後之排出水期間未特別限定，以 設定足以將滯留於離子交換裝置52a或52b内之污染水排出 之期間為佳。 15 200938491 [0051]根據本實施形態，由於可交換切換2個離子交換 裝置52a、52b而通水，故可在不停止對使用點61之超純水 之供水下’連續去除過氧化氫。 [0052] 5 (第3實施形態） 使用第3圖，就本發明之過氧化氫除去裝置之第3實施 形態作説明。 第3圖係顯示第3實施形態之臭氧水製造裝置11 〇之节 程圖。本實施形態係於第1圖所示之第1實施形態之過氧化 10 氫除去裝置53的二次侧設置臭氧溶解裝置54，於該臭氧溶 解裝置54連接臭氧產生裝置56者。 [0053]臭氧溶解裝置54未特別限定，有藉由氣體透過 膜，使臭氧氣體溶解於水中之膜溶解裝置、使臭氡氣體而 溶解於水中之裝置、藉由’使臭氧氣體於水中起泡而溶解 15 之裝置、將臭氧氣體供給至泵之上游側，以泵内之授摔使 臭氧氣體溶解之裝置等。用於上述膜溶解之氣體透過膜以 可承受臭氧之強氧化力之親1樹脂系疏水性多孔質媒為佳。 又，臭氧產生裝置56未特別限定，有藉由無聲放電或電解 法等之臭氧產生器。 2〇 [0054]就本實施形態之水中之過氧化氫除去方法、臭氧 水之製造方法作說明。 以過氧化氫除去裝置53處理以次系統40製造之超純 水，去除過氧化氫。將以臭氧產生裝置56製造之臭氧氣體 送至臭氧溶解裝置54。以臭氧溶解裝置54將臭氧氣體溶解 16 200938491 於業經去除過氧化氫之水。將預定濃度之臭氧業經溶解於 水中之臭氧水供給至使用點66。 [0055] 在本實施形態中，臭氧濃度未特別限定’以依使 用點66之用途設定為佳，舉例言之，依用途，以在1 ·〜lOOppm 5 之範圍設定為佳。 [0056] 根據本實施形態，由於可使用業經去除過氧化氫 之水，故可抑制所得之臭氧水中之臭氧之自分解。結果， 臭氧水中之臭氧濃度穩定。又，可穩定地將高濃度臭氧水 〇 供給至使用點。 1〇 [0057] (第4實施形態） 使用第4圖，就本發明之過氧化氫除去裝置之第4實施 形態作說明。第4圖係第4實施形態之臭氧水製造裝置120之 流程圖。本實施形態係將第3圖所示之第3實施形態之過氧 15 化氫除去裝置53變更成將離子交換裝置52a、52b並排配置 之過氧化氫除去裝置55者。 ❹ [0058]就本實施形態之水中之過氧化氫除去方法、臭氧 水之製造方法作說明。 以過氧化氫除去裝置55處理以次系統4〇製造之超純 2〇 水，去除過氧化氫。將以臭氧產生裝置56製造之臭氧氣體 送至臭氧溶解裝置54。以臭氧溶解裝置54將臭氧氣體溶 解’將溶解有預定濃度之臭氧之水供給至使用點67。 [〇〇59]根據本實施形態’由於可交互切換2個離子交換 裝置52a、52b而通水，故可連續去除水中之過氧化氫。結 17 200938491 果可將臭氧濃度穩定之臭氧水 穩定且連續地將高濃度臭氧水 [0060] 連續供給至使用點。 供給至使用點。 又，可 5 (其他實施形態） 本發明之過氧化氫除去方法 於上述實施形態。 及過氧化氫除去裝置不限 10 * W施形態中，將次系⑽之UF裝置㈣ 口之分歧水(超純水)作為被處理水，通過各離子交換裝置 然而，被處理水不限於該分歧水，只要為含有過氧化^ 水即可。舉财之，可為料線氧化裝置46、非再生型痛 子交換裝置48之出口水，亦可為槽所承接之以次系統刪 造之水。再者’亦可為一次系統20之水。6 200938491 Parts of manufacturing equipment. Advantageous Effects of Invention [0015] According to the hydrogen peroxide removal method of the present invention, hydrogen peroxide can be effectively removed from water containing hydrogen peroxide by an ion exchange device for a long period of time. 5 Brief Description [0016] FIG. 1 shows the first aspect of the present invention. A flow chart of an ultrapure water production apparatus according to an embodiment. Q Fig. 2 is a flowchart showing 10 of the ultrapure water producing apparatus according to the second embodiment of the present invention. Fig. 3 is a flow chart showing the ultrapure water producing apparatus according to the third embodiment of the present invention. Fig. 4 is a flow chart showing the ultrapure water producing apparatus according to the fourth embodiment of the present invention. 15 Fig. 5 is a flow chart of a conventional ultrapure water manufacturing apparatus. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Fig. 1 is a flow chart showing an ultrapure water producing apparatus 8 according to an embodiment of the present invention. Further, in the present invention, "pure water" includes "ultra-pure water". [0019] The ultrapure water production apparatus 8 is a hydrogen peroxide removal apparatus 53 which is composed of one ion exchange unit 52, an on-off valve 51, and a control unit 7 200938491 70 in the ultrapure water production apparatus 210 shown in FIG. The conventional processing system, the pure water system 2, the secondary system 40, and the hydrogen peroxide removing device 53 are configured. The shut-off valve 51 and the ion exchange device 52 are sequentially disposed between the system 4 〇 and the use point 6 G. Further, the secondary system 40 is connected to each of the use points 62, 64. 5 [Face] Pre-treatment secret 1G sequentially set the original water tank 12, condensation and condensation, 14, filtration, device 16, transition water. The pre-treatment secret 10 removes the suspended matter or colloidal substance contained in the raw water of the raw water tank 12. The raw water ^ 12, the condensed sediment 14 , the excess 16 , and the filtered water tank 18 are not particularly limited, and an existing device can be used. 1〇 [0021] The primary pure water system 20 is provided with an ion exchange device 22, an ultraviolet irradiation device 24, a precision filtration membrane device 26, an RO membrane device 28, and a degassing device 30 in this order. The ion exchange barrier 22 is filled with an ion exchanger. The filling form of the ion exchanger is not particularly limited, and may be in the form of a single bed of an anion exchanger or a cation exchanger, or a mixed bed form of an anion exchanger and a cation exchanger, or a form of a bed. [0022] The ultraviolet irradiation device 24 is not particularly limited, and an existing device can be used. For example, there is an ultraviolet ray oxidizing device which can illuminate ultraviolet rays having a wavelength of around 185 nm in addition to ultraviolet rays having a wavelength of around 254 nm. An ultraviolet oxidizing device capable of strongly illuminating ultraviolet rays having a wavelength of around 185 nm is preferably used to decompose the TOC component contained in the filtered water obtained by the 20 pretreatment system. [0023] The fine filtration membrane device 26 is not particularly limited, and an existing device can be used. Further, the RO membrane device 28 is not particularly limited, and an existing device can be used. The gas removal device 30 is not particularly limited, and an existing device can be used. For example, it can be a vacuum degassing device or a membrane degassing device, etc., and the 4G system can increase the purity of the pure water obtained in the pure water system (4) to produce ultra-pure water. (4) The sequence is set to 5 ❹ 10 15 ❹ 20 times pure water tank 42, heat exchanger 44, line oxidizer 46, non-regeneration type ion exchange unit 448, and finally _ _ _ _ _ _ 4 can make water circulation. As long as the L-green Wei device 46 has the ability to effectively decompose the components of the dish in the pure water, it is not particularly desirable to manufacture an existing device. _6] The non-regeneration type ion exchange unit 48 can have an existing unit. Further, the non-regeneration type ion exchange unit 48 is filled with an ion exchanger. The filling form of the exchanger is not specified, and it is a single bed shape of an anionic tonic or a cation exchanger, and the existing bed form or the form of a bed of a sub-agent can be used in any form. - The pure water quality or the purpose of the ultra-pure water to the mosquito ride. Wide, money, batches to make the domain water to avoid the temperature, not limited, you can use the existing decoration. v TTr ^ can use the existing device. The media set 5〇 is not particularly limited, and [〇〇28] ion exchange (four) set 52 is not particularly limited as long as it is filled with a sputum-sub-exchange agent. It may be in the form of a single bed of the type _ shirt (four), a mixed bed form with other anion exchangers, or a mixed bed form or a double bed form with a cation exchange type. However, from the point of view of effectively removing the oxidation, it is better to fill the bed with a single bed. [0029] The OH-type anion exchanger can be a strong anion exchanger or a weak anion. However, from the viewpoint of improving the removal ability of hydrogen peroxide, it is preferred to select a strong alkaline exchanger. 9 200938491 [0030] The type of the OH-type anion exchanger is not particularly limited, and may be an ion exchange resin, an ion exchange fiber, or a monolithic porous ion exchanger. Among them, a highly versatile ion exchange resin should be used. Further, the shape of the ion exchange resin is not particularly limited, and may be a gel shape, a porous shape or a macropore shape. [0031] Further, the ion exchanger filled in the ion exchange device 52 may be of a regenerative type or a non-regeneration type. When the ion exchanger is regenerated, it may be contaminated, so it is installed at the point of use. In the present embodiment, the non-regeneration type is preferred. Further, the ion exchange unit 52 preferably has a venting valve on the secondary side. When the water is stopped, the water remaining in the apparatus is contaminated by the ion exchange ❾ 10 or the elution of the inner wall of the ion parenting device 52, which is the discharge of the contaminated water after the water is started. The hydrogen peroxide removing device 53 of the present embodiment is constituted by an ion exchange device 52, an on-off valve 51, and a control device 7A. [0033] "A mechanism for intermittently passing water containing hydrogen peroxide through an ion exchange device filled with an OH type 15 anion exchanger" means a control device for stopping the flow of water and water through the ion exchange device 52, as long as In order to have such a function, it is not specifically limited. For example, the control device 70 that is provided to the switch of the on-off valve 51 of the secondary side of the ion exchange device 52 or the ultra-pure water can be transported to the ion exchange at regular intervals. Control device for starting and stopping the pump of 20 device 52. Further, the opening and closing of the opening and closing of the pump and the start and stop of the pump can be performed automatically or manually. The method for producing ultrapure water and the method for removing hydrogen peroxide in ultrapure water according to the present embodiment will be described. [0035] In the pretreatment system 10, after the raw water tank 12 receives the raw water, the original 10 200938491 5 Ο 10 15 20 water is sequentially treated by the precipitation condensation tank 14 and the filtration device ι6, and the gel or suspended matter is mainly removed. And get filtered water. The obtained filtered water is stored in the filtration water tank 18. In a pure water system, the filtered water of the filtration tank 18 is adsorbed by the ion exchange unit 22 by the ion exchanger to remove the ion component or the TOC of the exchange ion is removed. [0036] Next, the filtered water is irradiated with ultraviolet rays by the ultraviolet irradiation device 24 to sterilize the filtered water or to decompose the T〇c component in the filtered water to the organic acid or even carbon dioxide (4). Then, the fine filter membrane device 26 and the RO membrane device 28 remove particulate matter or a decomposition product such as an organic acid generated by the ultraviolet irradiation device 24 and the like. In the step-by-step process, the permeated water-free gas device 3 is used to remove dissolved oxygen to obtain a pure water. [0037] In the secondary system, ultrapure water is obtained by further increasing the purity of the primary pure water obtained in one pure water system. The sub-pure water obtained by the secondary line is stored in the -th pure water tank 42. The pure water is heated to a predetermined temperature by the heat exchanger 44, and the purple oxidizing device 46 is subjected to ultraviolet rays to decompose the T〇C component in the water into a state of rich or even carbon dioxide. Further, during the irradiation of ultraviolet rays, hydrogenation of hydrogen is generated in water. Next, a non-regenerating ion-distributing ionizing wire of 48 is used and an organic acid or carbon dioxide generated by ultraviolet irradiation is used. [0038] The ultrafine water was obtained by removing the fine particles by the UF membrane device 5〇. Part of the ultrapure water obtained is sent directly to Lai 62, 64. X, the obtained super, drowning, and he partially passed through the ion exchange device 52, and contacted with the anion exchanger at G to remove hydrogen peroxide, and then delivered to (4) 6G. The other part of the ultrapure water is sent back to the secondary pure water tank 42, in the secondary system screw ring. After the water supply to the ion exchange unit 52 has been performed for a certain period of time from the secondary system 11 200938491 40, the on-off valve 51 is closed by the control unit 70 to stop the water flow. After the water is stopped, after a predetermined time elapses, the control device 70 opens the on-off valve 51, and then starts to pass water, and then the hydrogen peroxide removal in the ultrapure water is started. In this way, the water supply and the stop of the ion exchange device 52 5 are repeatedly performed. The flow rate of the ultrapure water to the ion exchange unit 52 is not particularly limited and may be determined depending on the capabilities of the ion exchange unit 52. For example, the space velocity (SV) with respect to the anion exchanger is preferably set in the range of 1 to 500 L/L-R.h-Ι, and is preferably set in the range of 10 to 100 L/L-R _ h-Ι. Further, the 1 〇 SV system is expressed by L/L-R · h-Ι with respect to the flow rate (L) of the unit volume of the ion exchanger. [0040] The water-passing period of the ion exchange device 52 of the present embodiment is not particularly limited, and the amount of hydrogen peroxide or the amount of treatment in the ultrapure water is considered to be arbitrary during the period in which the ability to maintain the concentration below the desired concentration is maintained. Set to be good. 15 Further, the water can be set for a certain period of time, and the amount of hydrogen peroxide can be measured on the secondary side of the ion exchange unit 52, and the time point of the constant concentration can be set as the end point of the water passage period. [0041] The period in which the water passing through the ion exchange device 52 is stopped is not particularly limited, and the amount of treatment of ultrapure water, the concentration of hydrogen peroxide in the ultrapure water, the size of the separation device 52, and the like can be set. The period during which the hydrogen peroxide removal capability of the ion exchange unit 52 is restored. For example, to treat ultrapure water containing 15 to 3 ppb of hydrogen peroxide, the hydrogen peroxide concentration is maintained below 1 〇 ppb, and the period during which the water is stopped is set in the range of 1 hour to 24 hours. good. Further, after the 12 200938491 contaminated water remaining in the ion exchange unit 52 is discharged immediately after the start of the water supply, it is preferable to supply the ultrapure water from which the peroxidized gas is removed to the use point. This is because it prevents contamination at the point of use. [0042] The ultra-pure water for removing the orbital hydrogen of the present invention is not particularly limited, and the resistivity is 15 Μ Ω·cm or more, and preferably 1 〇 or less. Also, the water temperature of 5 ultrapure water is not special. It is better to take 5~ thief, 15~ is better, 20~25°c is especially good. ‘ [0043] According to the state of the present invention, the chlorine removal capability of the ion exchange unit 52 can be recovered by stopping the passage of the ultrapure water to the ion exchange unit & Therefore, by repeatedly performing water supply and shutdown to the ion exchange unit 52, 10 can effectively remove hydrogen peroxide in the ultrapure water for a long period of time. (Second Embodiment) A second embodiment of the ammonia peroxide removing device of the present invention will be described with reference to Fig. 2'. Fig. 2 is a flow chart showing the ultrapure water producing apparatus of the second embodiment. In the present embodiment, the hydrogen peroxide removing device 53 of the first embodiment shown in Fig. 1 is changed to a hydrogen peroxide removing device 55 in which the ion exchange devices 52 & 52b are arranged in parallel. Further, in the hydrogen peroxide removing device 55 of the present embodiment, the ion exchange devices 52a and 52b are arranged side by side, the switching valve 5ia is connected to the primary side of the ion exchange device 52a, and the switching valve 51b is connected to the primary side of the ion exchange device 52b. Composition. Further, the control device 72 is connected to the on-off valves 51a and 52b. The flow paths on the primary side of the switching valves 51a and 51b are integrated into one flow path and connected to the secondary system 40. The secondary side flow paths of the ion exchange devices 52a and 52b are integrated into one flow path, and are connected to the use point 61. [0045] The "mechanism in which the water containing hydrogen peroxide is passed through 13 200938491 plural ion exchange device" in the present embodiment means a control device that alternately performs water supply and water stop of the ion exchange devices 52a and 52b, as long as In order to have such a function, it is not specifically limited. For example, it is also possible to alternately control the switching device 72 of the switching valves 5ia, 5 51b provided on the primary side of the ion exchange devices 52a, 52b at regular intervals or to perform water supply from the secondary system 4 to the ion exchange device. 52a, 52b pump start and stop control device. Further, the opening and closing of the switches of the on-off valves 51a and 51b and the start and stop of the pump can be performed automatically or manually. [0 (M6) A method for producing ultrapure water according to the present embodiment and a method for removing 10 hydrogen peroxide in ultrapure water will be described. [0047] Ultrapure water produced by a secondary system is passed through an ion exchange device. 52a, after the hydrogen peroxide is removed, it is supplied to the point of use 61. After the ion exchange device 52a has passed through the water for a certain period of time, the switching device 5ib is opened by the control device 72, and the water is turned on to the ion father changing device 52b. The water treated by the ion exchange unit 52b 15 is not supplied to the use point 61. On the other hand, the supply of the water treated by the ion exchange unit 52a to the use point 61 is continued. After the _ set period, the discharge of the ion exchange unit 52b is stopped. Water, the water treated by the ion exchange unit 52b is supplied to the use point 61. Then, the control unit 72 closes the on-off valve 51a to stop the water supply to the ion exchange unit 52a. This is performed, and the 2-inch wide-sub-exchange unit 52a is removed. The hydrogen peroxide removal is switched to the hydrogen peroxide removal of the ion exchange unit 52b. [0048] After the ion exchange unit 52b is in the water for a certain period of time, the control unit 72 opens the on-off valve 51a to start the ion exchange apparatus. At the same time, the water treated by the ion exchange device 52a is not supplied to the use point 61 and is discharged into the use point 61. The second aspect of the process is to continue to use the water to be used by the ion exchange device. After the beam, the row of the ion exchange device 52a is stopped - the ion exchange device is treated, and the water is supplied to the point of use 6 to connect 5 10 15 ❹ 20 = the control device 72 turns off the -51b, and stops the water supply to the ion exchange device. Thus, the 'pass water transfer by the ion exchange devices 52a and 52b' is repeated to remove the hydrogen peroxide in the ultrapure water, and the ultrapure water from which the chlorine peroxide has been removed is sent to the use point 61. Tao 9] ion exchange device 52a and 52b can be used in the case of the ion-supporting I-input 52 of the embodiment of the present invention. The amount of hydrogen peroxide and the amount of treatment of the ultrapure water towel are considered in the case where the ion is placed in the water and the water is not in the special period. Alternatively, during the recovery of the hydrogen peroxide removal by the ion exchange devices 52a and 52b, the water can be maintained in a room where the ability to remove the hydrogen peroxide of the ultrapure water towel to less than (four) degrees is maintained. During the period, after the scheduled period, the passage can be stopped. The amount of hydrogen peroxide may also be measured on the secondary side of the ion exchange devices 52 &, 52b, and the water flow may be stopped at a point in time when a certain concentration is reached. [0050] The period of stopping the passage of water to the ion exchange devices 52a, 52b is not In particular, the period in which the hydrogen peroxide removal ability is restored can be set in consideration of the treatment amount of ultrapure water, the hydrogen peroxide concentration in the ultrapure water, the scale of the ion exchange devices 52a and 52b, etc. For example, the treatment is contained. 15 to 3 〇 ppb of ultra-pure water of peroxidized mice, maintaining the concentration of peroxidation below 1 〇 ppb, preferably in the range of 1 hour to 24 hours. Further, during the discharge of the ion exchange devices 523 and 52b, the discharge water after the restart of the water is not particularly limited, and it is preferable to set a period sufficient to discharge the contaminated water retained in the ion exchange device 52a or 52b. According to the present embodiment, since the two ion exchange devices 52a and 52b can be exchanged and water is exchanged, the hydrogen peroxide can be continuously removed without stopping the supply of the ultrapure water at the use point 61. (Embodiment 3) A third embodiment of the hydrogen peroxide removing apparatus of the present invention will be described with reference to Fig. 3. Fig. 3 is a block diagram showing the ozone water producing apparatus 11 of the third embodiment. In the present embodiment, the ozone dissolving device 54 is provided on the secondary side of the peroxygen-hydrogen removing device 53 of the first embodiment shown in Fig. 1, and the ozone generating device 54 is connected to the ozone generating device 54. The ozone dissolving device 54 is not particularly limited, and is a device for dissolving ozone gas in water by means of a gas permeable membrane, a device for dissolving odorous gas in water, and by bubbling ozone gas in water. In the device for dissolving 15, the ozone gas is supplied to the upstream side of the pump, and the ozone gas is dissolved by the pump in the pump. The gas permeation membrane used for the dissolution of the above-mentioned membrane is preferably a pro-resin-based hydrophobic porous medium which can withstand the strong oxidizing power of ozone. Further, the ozone generating device 56 is not particularly limited, and there is an ozone generator such as a silent discharge or an electrolytic method. 2〇 [0054] A method for removing hydrogen peroxide in water and a method for producing ozone water according to the present embodiment will be described. The ultrapure water produced by the subsystem 40 is treated with a hydrogen peroxide removing device 53 to remove hydrogen peroxide. The ozone gas produced by the ozone generating device 56 is sent to the ozone dissolving device 54. The ozone gas is dissolved by the ozone dissolving device 54. 16 200938491 The water of hydrogen peroxide is removed. The ozone concentration of the predetermined concentration is supplied to the use point 66 via the ozone water dissolved in the water. In the present embodiment, the ozone concentration is not particularly limited. It is preferably set according to the use point of the use point 66. For example, it is preferable to set it in the range of 1 · lOOppm 5 depending on the application. According to the present embodiment, since the water from which hydrogen peroxide is removed can be used, the self-decomposition of ozone in the obtained ozone water can be suppressed. As a result, the ozone concentration in the ozone water is stable. Further, high-concentration ozone water hydrazine can be stably supplied to the point of use. (Fourth Embodiment) A fourth embodiment of the hydrogen peroxide removing apparatus of the present invention will be described with reference to Fig. 4. Fig. 4 is a flow chart showing the ozone water producing apparatus 120 of the fourth embodiment. In the present embodiment, the peroxygenation hydrogen removal device 53 of the third embodiment shown in Fig. 3 is changed to a hydrogen peroxide removal device 55 in which the ion exchange devices 52a and 52b are arranged side by side. ❹ [0058] A method for removing hydrogen peroxide in water and a method for producing ozone water according to the present embodiment will be described. Hydrogen peroxide is removed by treating the ultrapure 2 Torr water produced by the secondary system 4 with a hydrogen peroxide removing device 55. The ozone gas produced by the ozone generating device 56 is sent to the ozone dissolving device 54. The ozone gas is dissolved by the ozone dissolving device 54. The water in which the predetermined concentration of ozone is dissolved is supplied to the use point 67. According to the present embodiment, since the two ion exchange devices 52a and 52b can be alternately switched to pass water, the hydrogen peroxide in the water can be continuously removed. Conclusion 17 200938491 It is possible to continuously and continuously supply high-concentration ozone water [0060] to the point of use by stabilizing ozone water having a stable ozone concentration. Supply to the point of use. Further, 5 (other embodiment) The hydrogen peroxide removing method of the present invention is the above embodiment. And the hydrogen peroxide removing device is not limited to the 10* W embodiment, and the divergent water (ultra-pure water) of the UF device (4) of the sub-system (10) is used as the water to be treated, and the treated water is not limited to the treated water. Divided water, as long as it contains peroxide. For the sake of money, it may be the outlet water of the line oxidizing device 46, the non-regeneration type pain exchange device 48, or the water deleted by the tank system. Furthermore, it can also be the water of the system 20 once.
15 、[刪1]在第1〜㈣施形態中，將次系統40之分歧水輸 送至各使賴之間，配置過氧化氫除去裝置Μ或Μ，配置 處不限於此’舉例言之’亦可於非再生型離子交換裝置48 設置諸如過氧錢除去裝£„或&之「使含㈣氧化氯之 水間歇地通過之機構」。又，亦可以如過氧化氫除去裝置％ 之形態設置「使含有過氧化氫之水交互通過複數離子交換 裝詈之嬙槿，。 '15、[Delete 1] In the first to (fourth) configuration, the divergent water of the secondary system 40 is transported between the respective dams, and the hydrogen peroxide removing device Μ or Μ is disposed, and the configuration is not limited to this 'exemplary' It is also possible to provide a mechanism for intermittently passing water containing (four) chlorine oxide, such as a peroxygen removal device, or a non-regeneration type ion exchange device 48. Further, it is also possible to provide "the hydrogen peroxide-containing water exchanges through the plurality of ion exchange devices in the form of a hydrogen peroxide removal device %."
20 [0062] 在第2、第4實施形態中’將2個離子交換裝置 52a、52b並排配置作為過氧化氫除去|置55，該離子錢 裝置亦可為3個以上。宜考慮水之處理量、離子交換裝置 52a、52b内之離子交換劑之能力，決定設置台數。 [0063] 第1〜第4實施形態之前處理系統10、-次純水系 18 200938491 統20、次系統40為一例，非限於上述實施形態者。可使用 上述以外之裝置，亦可使用其他組合。 [0064] 在第1〜第4實施形態中，於離子交換裝置52之一 次側設置開關閥51，於離子交換裝置52a、52b之一次侧設 5 置開關閥51a、51b，各開關閥之設置處不限於此，亦可設 置於離子交換裝置52、52a、52b之二次側。 [0065] 在第卜第2實施形態中，以離子交換裝置52或者 離子交換裝置52a或52b將業經去除過氧化氫之水直接輸送 © 至使用點’亦可於離子交換裝置52、52a、52b之二次側設 10 置其他裝置。特別是宜設置用以去除微粒子之過濾臈裝置 (微濾器裝置或UF裝置）。因對各離子交換裝置之送水、停 止等，有從開關閥等產生灰塵之虞，而此舉可去除產生之 微粒子之故。又，第3、第4實施形態亦同樣地，於離子交 換裝置52、52a、52b之二次侧設置其他裝置、特別是用以 !5 去除微粒子之過濾膜裝置。 【實施例】 ® [0066]以下，就本發明以實施例為例，具體說明，但非 以實施例限定者。 (第1實施例） 20 於丙烯基製管柱填充100mL、層高200mm之羅門哈斯 (Rohm and Haas)公司製離子交換樹脂、AMBERJET4〇〇2 (〇H)(OH型強鹼性陰離子交換樹脂、凝膠型），而獲得離子 交換裝置A。將20〜25。(：、過氧化氫濃度15〜30ppb之水以 SV=50L/L-R . h-Ι通過所獲得之離子交換裝置a。於通水 19 200938491 開始2小時後，關閉離子父換裝置A之一次側之開關閥，停 止通水，放置5小時。放置5小時後’再度進行通水2小時。 如此，以2小時通水/5小時停止通水之週期，進行1〇天之 連續通水，而獲得處理水。對通水開始29小時後（通水時 5 間.總計：9小時、通水量_ BV(通水量相對於離子交換裝置 之樹脂體積=體積倍)=450)及1〇天後(通水時間總計：仰小 時、通水量：BV=3400)而得之處理水，進行過氧化氫水 濃度之測量。將其測量值顯示於表1。此外，本實施例之 水係將一次純水以熱交換器、膜式除氣裝置、紫外線氧化 ❹ 10 裝置、非再生蜜離子交換裝置、UF裝置之順序通水，處理 而得之電阻率= 18ΜΩ . cm以上，TOC=lppb以下之超純水 (之後，在第2〜第4實施例及第1、第2比較例中相同）。 [0067] (第2實施例） · 15 於丙烯基製管柱填充l〇〇mL、層高200mm之羅門哈斯[Embodiment 2] In the second and fourth embodiments, the two ion exchange devices 52a and 52b are arranged side by side as the hydrogen peroxide removal|disconnection 55, and the ion exchange device may be three or more. The amount of water to be treated and the capacity of the ion exchanger in the ion exchange units 52a and 52b should be considered, and the number of units to be set should be determined. In the first to fourth embodiments, the pre-processing system 10, the sub-pure water system 18, the 200938491 system 20, and the sub-system 40 are examples, and are not limited to the above embodiments. Other than the above, other combinations may be used. In the first to fourth embodiments, the on-off valve 51 is provided on the primary side of the ion exchange device 52, and the on-off valves 51a and 51b are provided on the primary side of the ion exchange devices 52a and 52b, and the respective on-off valves are provided. The present invention is not limited thereto, and may be provided on the secondary side of the ion exchange devices 52, 52a, 52b. In the second embodiment, the water having been subjected to hydrogen peroxide removal is directly transported to the point of use by the ion exchange device 52 or the ion exchange device 52a or 52b. The ion exchange devices 52, 52a, 52b may also be used. On the secondary side, 10 sets other devices. In particular, it is preferable to provide a filtering device (microfilter device or UF device) for removing fine particles. Since water is supplied to the ion exchange devices, the like, and the like, dust is generated from the on-off valve or the like, and the generated microparticles can be removed. Further, in the third and fourth embodiments, similarly, other devices, particularly a filter film device for removing fine particles, are provided on the secondary side of the ion exchange devices 52, 52a, and 52b. [Examples] Hereinafter, the present invention will be specifically described by way of examples, but not by way of examples. (First Embodiment) 20 An ion exchange resin (AMHJET4〇〇2 (〇H) manufactured by Rohm and Haas Co., Ltd.) was filled with 100 mL of a propylene-based pipe column and a height of 200 mm (OH type strong basic anion exchange) Resin, gel type), and ion exchange device A was obtained. Will be 20~25. (:, the water with a hydrogen peroxide concentration of 15~30ppb is passed through the obtained ion exchange device a at SV=50L/LR. h-Ι. After 2 hours from the beginning of the water 19 200938491, the primary side of the ion-parent replacement device A is turned off. The on-off valve, stop the water, and let it stand for 5 hours. After 5 hours of placement, 'the water is re-circulated for 2 hours. So, the water-passing cycle is stopped by 2 hours of water/5 hours, and the continuous water is passed for 1 day. Obtained treated water. 29 hours after the start of water supply (5 times when water is passed. Total: 9 hours, water flow _ BV (water volume relative to resin volume of ion exchange device = volume times) = 450) and 1 day later The treated water obtained by the total of the water passing time: the hour of the water flow, the water flow rate: BV = 3400, was measured for the concentration of the hydrogen peroxide water. The measured values are shown in Table 1. In addition, the water system of the present embodiment will be once Pure water is passed through water in the order of heat exchanger, membrane degassing device, ultraviolet yttrium oxide 10 device, non-regeneration honey ion exchange device and UF device. The resistivity is more than 18ΜΩ·cm, and TOC=lppb or less. Ultrapure water (hereinafter, in the second to fourth embodiments and the first and second comparative examples) The same). [0067] (Example 2) in 15-column filled l〇〇mL propenyl made, the height of 200mm Haas
公司製離子交換樹脂、AMBERLITEIRA90〇(〇H)(OH型強 驗性陰離子交換樹脂、巨孔型），而獲得離子交換裝置B。 D 以下’與第1實施例同樣地，進行10天之連續通水，而獲 得處理水。測量於通水開始29小時後(通水時間總計：9小 20 時、通水量：BV=450)及10天後(通水時間總計：68小時、 通水量：BV=3400)而得之處理水之過氧化氫水濃度，於 表1顯示其結果。 [0068] (第1比較例) 20 200938491 將20〜25 t、過氧化氫濃度15〜3〇ppb之水以 SV=50L/L_R · hel通過在第丨實施例所得之離子交換裝置 A。 測量通水開始30分鐘後(BV=25)及24小時後(BV=12〇〇) 之處理水中之過氧化氫水濃度，於表1記載其結果。 5 ❹ 10 15 20 [0069] (第2比較例） 將20〜25。(：、過氧化氫濃度15〜3〇ppb之水以 SV=50L/L-R . h-Ι通過在第2實施例所得之離子交換裝置 B。 測量通水開始30分鐘後(BV=25)及24小時後(bv=12〇〇) 之處理水中之過氧化氫濃度’於表1記載其結果。 [0070] (第3實施例) 在第1比較例，於通水24小時後，停止對離子交換裝置 A之通水3天。之後’以SV=50L/L-R· h-Ι再度開始通過2〇 〜25t：、過氧化氫濃度15〜30ppb之水。測量通水再開始3〇 分鐘後之處理水中之過氧化氫濃度，於表2顯示其、妹果。 [0071] (第4實施例） 在第2比較例’於通水24小時後’停止對離子交換裝置 B之通水3天。之後，以SV=50L/L-R · h-Ι再度開始通過2〇 〜25。(：、過氧化氫濃度15〜3〇PPb之水。測量通水再開始3〇 分鐘後之處理水中之過氧化氫濃度’於表2顯示其結果。 [0072] (第5實施例) 21 200938491 於G5咼壓罐（ORGANO股份有限公司製）填充5L之羅門 哈斯社製離子交換樹脂、AMBERJET4002(OH)，而獲得離 子交換裝置C。接著，通過過氧化氫濃度15〜2〇ppb之水以 流量2001711(8'¥=40171^-尺.11-1)，而獲得處理水。接著，以 5 JAPAN GORE-Tex股份有限公司製、GM-02RES(臭氧溶解 膜模組)將臭氧氣體溶解於所得之處理水中，製造臭氧水。 測量臭氧水開始製造3小時後及4天後之處理水中之過氧化 氫濃度、臭氧水中之臭氧濃度，於表3顯示其結果。此外， 本實施例之水係將一次純水以紫外線氧化裝置、非再生型 ❿ 1〇 混合床式離子交換裝置、UF膜裝置之順序通過，處理而得 之電阻率=18ΜΩ. cm以上，TOC=lppb以下之超純水（之後， 在第3比較例中相同）。 [0073] ' (第3比較例） · 15 以除了不將過氧化氫濃度15〜20ppb之水通過離子交 換裝置C外，其他與第5實施例相同之條件製造臭氧水。測 量臭氧水’製造4天後之處理水巾之過氧化氫濃度、从 〇 水中之臭氧濃度，於表3顯示其結果。 [0074] 20 (過氧化氫濃度） 超純水中之低濃度過氧化氫之定量方法以眾所周知之 法、例如日本專利公開公報昭56.54582號記載之方法為標準。 [0075] (臭氧濃度之測量） 22 200938491 臭氧濃度之測量係使用攜帶式溶解臭氧濃度計(OM-10 1P-30、APPLICS股份有限公司製），以紫外線吸光光度法測量。 [0076] 【表1】 第1實施例 第2實施例 第1比較例 第2比較例 離子交換裝置通水前 之過氧化氫濃度(ppb) 15-30 15-30 15-30 15-30 通水30分鐘後之過氧 化氫濃度(ppb) - - <1 <1 通水24小時後之過氧 化氫濃度(ppb) - - 10.9 11.1 通水29小時後之過氧 化氫濃度(ppb) 3.9 6.2 華 - 通水10天後之過氧化 氫濃度(ppb) 3.7 7.6 - - 5 [0077] 【表2】 第3實施例 第4實施例 離子交換裝置通水前之 過氧化氫濃度(ppb) 15-30 15-30 通水30分鐘後之過氧化氫 濃度(ppb) <1 <1 10 [0078] 【表3】 第5實施例 過氧化氫 濃皮(ppbj 臭氧濃度 (PPm) 換裝置通水前之水 15-20 0、 -¾杏製造開始3小時後 1.5 47、 製造4天後 6.6 41 第3比較例 過氧化氫 濃度(ρρΐό 臭氧濃度 (ppm) 15-20 0 - - 18.1 32 23 200938491 [0079] 從表丨之結果可知，第丨、第2實施例於通水開始 29小時後(BV=450)、通水開始1〇天後(Bv=34〇〇)處理水中之 過氧化氫濃度皆抑制低至相同之水準。另一方面，在第j、 第2比較例中，通水24小時後(BV=12〇〇)，過氧化氫濃度超 5過10PPb。從此可知，藉間歇進行水之對離子交換裝置之通 過，可在不降低〇H型陰離子交換樹脂之過氧化氫除去能力 下進行過氧化氫之除去。從表2之結果可知，確認了即使 為第1、第2比較例中用於過氧化氫除去之離子交換裝置， 藉停止通水，亦可恢復0H型陰離子交換樹脂之過氧化氫除 ❹ 10 去能力。 [0080] 如表3之結果，在第5實施例中藉使用以對離子交 換裝置之通水，去除過氧化氫之處理水，製造臭氧水，在 臭氧水製造開始4天後，處理水仍維持在1〇ppb以下之過氧 ’ 化氫濃度，而臭氧水之臭氧濃度亦超過仙卯瓜。 - 15 [0081]另一方面，在第3比較例中，由於未使被處理水 通過離子交換裝置，故水中之過氧化氫濃度在高水準。以 此種水製造之臭氧水之臭氧濃度低於第5實施例。從此及第 u 1〜第4實施例之結果表示藉反覆進行對離子交換裝置之通 水、停止，去除水中之過氧化氫，可獲得長期穩定濃度之 2〇 臭氧水’進而獲得高濃度之臭氧水。 [0082]根據本發明之過氧化氫除去方法，由於可使含有 過氧化氫之水間歇地通過離子交換裝置，故配置複數個離 子交換裝置時，含有過氧化氫之水交互通過，而可長期有 效地從含有過氧化氫之水去除過氧化氫。 24 200938491 【圖式簡單說明】 第1圖係顯示本發明第1實施形態之超純水製造裝置之 流程圖。 第2圖係顯示本發明第2實施形態之超純水製造裝置之 5 流程圖。 第3圖係顯示本發明第3實施形態之超純水製造裝置之 流程圖。 第4圖係顯示本發明第4實施形態之超純水製造裝置之 流程圖。 10 第5圖係習知一般超純水製造裝置之流程圖。 【主要元件符號說明】 8，100，210...超純水製造裝置 10.. .前處理系統 12···原水槽 14…凝結沉澱裝置 16…過濾裝置 18…過濾水槽 20.. .—次純水系統 22…離子交換裝置 24.. .紫外線照射裝置 26.. .精密過濾膜裝置 28…逆滲透(RO)裝置 30...除氣裝置 25 200938491 40.. .二次純水系統(次系統） 42…一次純水槽 44.. .熱交換器 46…紫外線氧化裝置 48…非再生型離子交換裝置 50.. .最終過濾器(UF)裝置 51，51a，51b._.開關閥 52，52a，52b...離子交換裝置 53，55…過氧化氫除去裝置 54…臭氧溶解裝置 56.. .臭氧產生裝置 60，61，62，64，66，67，250，252，254...使用點 70，72...控制裝置 110，120...臭氧水製造裝置The company's ion exchange resin, AMBERLITEIRA 90 〇 (〇H) (OH type strong anion exchange resin, macroporous type), and ion exchange device B were obtained. D is the same as in the first embodiment, and water is continuously supplied for 10 days to obtain treated water. The measurement was carried out 29 hours after the start of the water supply (total time of water flow: 9 hours 20 hours, water flow rate: BV=450) and after 10 days (total water flow time: 68 hours, water flow rate: BV=3400) The water hydrogen peroxide water concentration is shown in Table 1. (First Comparative Example) 20 200938491 Water of 20 to 25 t and a hydrogen peroxide concentration of 15 to 3 ppb was passed through the ion exchange apparatus A obtained in the second embodiment at SV = 50 L/L_R·hel. The hydrogen peroxide water concentration in the treated water after 30 minutes from the start of the water flow (BV = 25) and 24 hours (BV = 12 Torr) was measured, and the results are shown in Table 1. 5 ❹ 10 15 20 [0069] (2nd comparative example) 20 to 25 will be used. (:, water having a hydrogen peroxide concentration of 15 to 3 ppb is SV = 50 L/LR. h-Ι is passed through the ion exchange device B obtained in the second embodiment. After measuring the water supply for 30 minutes (BV = 25) and The hydrogen peroxide concentration in the treated water after 24 hours (bv = 12 〇〇) is shown in Table 1. [0070] (Third Example) In the first comparative example, after 24 hours of water passing, the pair was stopped. The ion exchange device A was passed through water for 3 days. Then, the water was passed through 2〇~25t: and the hydrogen peroxide concentration was 15~30ppb at SV=50L/LR·h-Ι. After measuring the water for another 3 minutes, The concentration of hydrogen peroxide in the treated water is shown in Table 2. [0071] (Fourth Embodiment) In the second comparative example, 'the water is passed to the ion exchange device B after 24 hours of water passing through After that, start with SV=50L/LR · h-Ι again by 2〇~25. (:, hydrogen peroxide concentration 15~3〇PPb water. Measure the water after 3 minutes of water treatment. The results of the hydrogen peroxide concentration are shown in Table 2. [0075] (5th embodiment) 21 200938491 A 5L Rohm and Haas company ion was filled in a G5 pressure tank (manufactured by ORGANO Co., Ltd.) The resin, AMBERJET4002(OH) was exchanged, and the ion exchange device C was obtained. Then, the water was treated with a hydrogen peroxide concentration of 15 to 2 ppb at a flow rate of 2001711 (8'¥=40171^-foot.11-1). Next, ozone gas was dissolved in the obtained treated water by GM-02RES (Ozone Dissolving Membrane Module) manufactured by 5 JAPAN GORE-Tex Co., Ltd. to produce ozone water. Measurement of ozone water started 3 hours later and 4 days. The hydrogen peroxide concentration in the treated water and the ozone concentration in the ozone water are shown in Table 3. In addition, the water system of the present embodiment uses a UV oxidizing device and a non-regenerating ❿ 1〇 mixed bed ion in the primary pure water. The order of the exchange device and the UF membrane device was obtained by treatment, and the resistivity was 18 Ω·cm or more, and the ultrapure water having a TOC of 1 ppb or less (the latter was the same in the third comparative example). [0073] Example) 15 Ozone water was produced under the same conditions as in the fifth embodiment except that water having a hydrogen peroxide concentration of 15 to 20 ppb was not passed through the ion exchange apparatus C. The ozone water was measured and the treated water towel was manufactured 4 days later. Hydrogen peroxide concentration, from drowning The ozone concentration is shown in Table 3. [0074] 20 (Hydrogen peroxide concentration) The method of quantifying the low-concentration hydrogen peroxide in the ultrapure water is a well-known method, for example, the method described in Japanese Patent Laid-Open Publication No. Sho 56.54582 [0075] (Measurement of Ozone Concentration) 22 200938491 The ozone concentration was measured by a UV spectrophotometry using a portable dissolved ozone concentration meter (OM-10 1P-30, manufactured by APPLICS CORPORATION). [Table 1] First Embodiment Second Embodiment First Comparative Example Second Comparative Example Ion Exchange Device Hydrogen Peroxide Concentration (ppb) 15-30 15-30 15-30 15-30 Hydrogen peroxide concentration after 30 minutes of water (ppb) - - <1 <1 Hydrogen peroxide concentration (ppb) after 24 hours of water flow - - 10.9 11.1 Hydrogen peroxide concentration (ppb) after 29 hours of water passage 3.9 6.2 Huashui - Hydrogen Peroxide Concentration (ppb) after 10 days of water 3.7 7.6 - - 5 [Table 2] The hydrogen peroxide concentration before the water passing through the ion exchange device of the fourth embodiment of the third embodiment (ppb) 15-30 15-30 Hydrogen peroxide concentration (ppb) after 30 minutes of water passage <1 <1 10 [Table 3] The fifth embodiment of hydrogen peroxide rich skin (ppbj ozone concentration (PPm) Change the water before the device is 15-20 0, -3⁄4 apricot is manufactured 3 hours after the start of 1.5 47, after 4 days of manufacture 6.6 41 The third comparative example hydrogen peroxide concentration (ρρΐό ozone concentration (ppm) 15-20 0 - - 18.1 32 23 200938491 [0079] From the results of the expression, it can be seen that the second and second embodiments are treated in the water after 29 hours from the start of the water supply (BV=450) and one day after the start of the water (Bv=34〇〇). Hydrogen peroxide The concentration was suppressed to the same level. On the other hand, in the jth and second comparative examples, after 24 hours of water passage (BV=12〇〇), the hydrogen peroxide concentration exceeded 5 times 10 ppm. By passing the water-to-ion exchange device, the hydrogen peroxide can be removed without lowering the hydrogen peroxide removal ability of the 〇H-type anion exchange resin. From the results of Table 2, it was confirmed that the first and second were confirmed. In the ion exchange apparatus for hydrogen peroxide removal in the comparative example, the hydrogen peroxide removal ability of the 0H type anion exchange resin can be recovered by stopping the water flow. [0080] As shown in Table 3, in the fifth embodiment In the example, by using water to the ion exchange device, the treated water of the hydrogen peroxide is removed to produce ozone water, and after 4 days from the start of the ozone water production, the treated water is maintained at a hydrogen peroxide concentration below 1 〇 ppb. The ozone concentration of ozone water is also higher than that of the genus melon. - 15 [0081] On the other hand, in the third comparative example, since the water to be treated is not passed through the ion exchange device, the concentration of hydrogen peroxide in the water is at a high level. Ozone produced from such water The ozone concentration is lower than that of the fifth embodiment. From the above, the results of the first to fourth embodiments show that the water supply to the ion exchange device is stopped and stopped, and the hydrogen peroxide in the water is removed to obtain a long-term stable concentration. Ozone water's in turn to obtain high concentrations of ozone water. According to the hydrogen peroxide removal method of the present invention, since the water containing hydrogen peroxide can be intermittently passed through the ion exchange device, when a plurality of ion exchange devices are disposed, the water containing hydrogen peroxide crosses through, and can be long-term. Effectively remove hydrogen peroxide from water containing hydrogen peroxide. [Brief Description of the Drawings] Fig. 1 is a flow chart showing the ultrapure water producing apparatus according to the first embodiment of the present invention. Fig. 2 is a flow chart showing the ultrapure water producing apparatus according to the second embodiment of the present invention. Fig. 3 is a flow chart showing the ultrapure water producing apparatus according to the third embodiment of the present invention. Fig. 4 is a flow chart showing the ultrapure water producing apparatus according to the fourth embodiment of the present invention. 10 Figure 5 is a flow chart of a conventional ultrapure water manufacturing apparatus. [Description of main component symbols] 8,100,210...Ultra-pure water manufacturing apparatus 10. Pretreatment system 12··· Raw water tank 14... Condensation sedimentation device 16...Filter device 18...Filter water tank 20.. Sub-pure water system 22...Ion exchange device 24.. UV irradiation device 26..Precision filtration membrane device 28...Reverse osmosis (RO) device 30...Degassing device 25 200938491 40.. .Second pure water system (Secondary system) 42... One-time pure water tank 44.. Heat exchanger 46... Ultraviolet oxidizing device 48... Non-regeneration type ion exchange unit 50.. Final filter (UF) unit 51, 51a, 51b._. 52, 52a, 52b... Ion exchange device 53, 55... Hydrogen peroxide removal device 54... Ozone dissolution device 56. Ozone generating device 60, 61, 62, 64, 66, 67, 250, 252, 254. .. use point 70, 72... control device 110, 120... ozone water manufacturing device