201235090 六、發明說明： 【發明所屬之技術領域】 本發明係有關硏磨劑之回收方法及回收裝置，特別是 有關可將使用完之硏磨漿料濃縮成高濃度之硏磨劑之回收 方法及使用此之回收裝置。 【先前技術】 形成於半導體晶圓上之絕緣膜，金屬薄膜等之被膜表 面係要求有高度之平坦面。爲了對應於此要求，而採用在 使硏磨漿料介入存在於硏磨墊片等之硏磨構件與半導體晶 圓之間的狀態進行硏磨之CMP (化學性機械硏磨： Chemical Mechanical Polishing) & 作爲在CMP所使用之硏磨劑，係使用分散性佳，粒子 徑一致之二氧化矽微粒子，或硏磨速度大之賽里阿聚脂纖 維，硬度高，安定之氧化鋁等。此等硏磨劑係作爲特定粒 子徑，濃度的粒子分散於水中之漿料，經由製造商所提供 。漿料係因應各現場，在供給至CMP機器時稀釋成特定濃 度所使用。 通常，對於此漿料中，係除硏磨劑之外，預先添加有 氫氧化鉀，氨，有機酸，胺類等之pH調整劑，界面活性 劑等之分散劑，過氧化氫，碘酸鉀，硝酸鐵（III )等之 氧化劑等。或者，此等成分則在硏磨時另外加以添加至漿 料。 此等之硏磨漿料係從使用量多且高價的點，另外，產 -5- 201235090 業廢棄物量降低的觀點，進行再利用則爲理想。但硏磨工 程排水係經由多數之洗淨工程水等而加以稀釋，硏磨劑濃 度則下降。加上，對於硏磨工程排水係混入有破壞半導體 晶圓’或被膜材料，硏磨墊屑，硏磨劑之細微粒子，或經 由硏磨劑產生凝結而產生之粒子徑大的固體不純物等。因 此’將如此之硏磨工程排水，以無處理作爲硏磨劑再利用 時’經由硏磨劑濃度之下降，加以平坦化之硏磨速度則下 降’以及於晶圓表面產生有傷痕而製品的產率則下降。 隨之’對於再利用，必須從硏磨排水進行粗大固體物 ’鹽類等之不純物的除去處理，更且進行濃縮處理，再調 整特定組成之硏磨漿料。 從以往，爲了 CMP工程排水處理，而嘗試種種技術之 開發。 例如，提案有將CMP工程排水，通水於精密過濾膜， 額外過濾膜等之分離膜進行膜處理，更且添加藥劑或超純 水，調製硏磨劑或分散劑的濃度，作爲硏磨劑漿料進行再 利用之方法。 例如，對於專利文獻1係揭示有以提升膜透過流速爲 目的，在第1之膜要素中，將循環液的漿料濃度維持爲特 定値進行膜分離之後，抽出其一部分，在第2之膜要素更 且進行膜分離之CMP排水的膜處理方法。 另外，對於專利文獻2係揭示有除去微細粒子凝結而 大徑化之凝結物，可回收所期望粒徑之硏磨劑粒子的半導 體用漿料狀硏磨液之分離方法。在專利文獻2中，以第1工 201235090 程之額外過濾膜1 m，除去微細粒子之同時，以第2工程之 精密過濾膜2m，除去成爲硏磨傷原因之粗大粒子。 更且，對於專利文獻3係揭示有將CMP工程的硏磨劑 廢液，使用額外過濾膜等之濃縮用過濾器而濃縮成原液的 比重之0.90倍〜0.96倍之後（一次濃縮工程），將此濃縮 液更濃縮至原液的比重之0.9 9倍〜1.0 1倍（二次濃縮工程 )，再利用硏磨劑之方法。 對於專利文獻4係揭示有降低對於膜分離手段之通水 量或排水中的分散劑量，抑制膜之早期的篩孔堵塞之硏磨 劑的回收裝置。在專利文獻4中係將由前段之第1之膜分離 手段所濃縮之濃縮液，導入至後段之第2之膜分離手段， 經由此第2之膜分離手段而除去粗大固體物。 在上述的例所使用之中空系型的分離膜係廣泛應用額 外過濾膜。中空系型的分離膜係爲了抑制其有效過濾長度 越長而使用之模組支數，而在成本面爲優越，通常係廣泛 使用lm程度之過濾長度的構成。 另一方面，在中空系型的分離膜中，隨著被處理水成 爲高濃度，於其內壁，固體成分則作爲膠凝而堆積，接著 膠凝的厚度增大。因此，膜的有效內徑則狹小化，而有壓 力損失之增大，和產生有膜的閉塞’而硏磨劑的回收率顯 著降低之虞。特別是對於CMP工程之排出水的處理情況’ 係硏磨劑濃度超過數％程度時，此傾向變爲顯著。因此， 實際上，至數％程度的濃縮則爲界限。在記載於上述專利 文獻的技術，對於將高濃度的被處理水通水的情況’係充 201235090 分抑制分離膜之篩孔堵塞，或伴隨於此之硏磨劑粒子的回 收率之下降之情況係爲困難。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開200 1 - 1 1 3 27 3號公報 [專利文獻2]日本特開平1 1 -283 3 8號公報 [專利文獻3]日本特開2008-34827號公報 [專利文獻4]日本特開2002-83789號公報 【發明內容】 [發明欲解決之課題] —般，在經由分離膜之過濾處理中，當被處理水濃度 超過特定値時，膜的篩孔堵塞之進行速度則急遽上升。如 先前所述，對於硏磨漿料之情況，係硏磨劑濃度超過數％ 程度時，篩孔堵塞則急遽進行。因此，在廢水處理等之以 往技術中，作爲固體成分之濃縮係實際上，數％程度爲界 限，在此程度的濃度之中，作爲硏磨漿料，直接對於CMP 工程進行再利用之情況係爲困難。 更且，使用中空系型的分離膜之情況，漿料中的硏磨 劑濃度濃縮至超過數％程度時，如先前所述，在中空系內 部中，接著膠凝的堆積則進行。之後更加繼續濃縮處理時 ，如圖8所示，明確了解到成爲凝膠狀之硏磨劑則堆積於 中空系之被處理水出口側。當成爲如此之狀態時，無法得 -8 - 201235090 到濃縮水，更且無法繼續使用模組本身。更且，因硏磨劑 堆積成凝膠狀之故，硏磨劑之回收率則急遽下降。 本申請發明係爲了解決上述課題所作爲之構成，其目 的爲提供抑制壓力損失之增大，或經由膜的閉塞的回收率 大幅度之降低，且硏磨劑可濃縮成高濃度之硏磨劑之回收 裝置及硏磨劑之回收方法。 [爲解決課題之手段] 爲了達成上述目的，本發明者進行銳意檢討時，如上 述，對於分離膜的過濾面上之膠凝的堆積，或在被處理水 出口側之硏磨劑的凝膠狀物質之堆積有無係發現主要依存 於分離膜之有效過濾長度者，至完成本申請發明。 本發明之硏磨劑之回收裝置係從在CMP工程所使用之 使用完的硏磨漿料，回收硏磨劑之裝置，其特徵爲前述硏 磨劑之回收裝置係具有導入前述使用完的硏磨漿料之孔道 爲圓筒狀之分離膜，前述分離膜之孔道係有效過濾部的長 度爲0.8m以下，前述硏磨劑之回收裝置係將前述使用完的 硏磨漿料之硏磨劑濃度，濃縮成1 〇質量％以上之濃度。 導入於前述分離膜之硏磨劑濃度係因依存於客戶工場 之排液濃度之故而未特別加以限定，但一般而言，可作爲 導入0.02〜5質量％之使用完的漿料的構成。對於前述分離 膜之中空部，係前述使用完的硏磨漿料則由叉流方式加以 通水爲佳。前述分離膜係設置於內壓型之膜分離部爲佳。 前述分離膜爲中空系膜爲佳。前述分離膜之內徑係0.1 mm -9- 201235090 以上0.8mm以下爲佳》前述分離膜之分劃分子量係3,000〜 3〇,〇 〇〇爲佳。前述分離膜係由聚乙烯，4氟化乙烯，聚偏 二氟乙烯，聚丙烯，醋酸纖維素，聚丙稀睛，聚醯亞胺， 聚楓或聚醚颯之任一加以構成爲佳。 前述硏磨劑之回收裝置係於前述分離膜之前段，具有 較此分離膜爲長之有效過濾長度，可作爲具有孔道爲圓筒 狀之前段分離膜者。前述前段分離膜之有效過濾部的長度 L1爲0.8〜1.5m，設置於前述前段分離膜之後段的後段分 離膜之有效過濾部的長度L2爲0.2〜0.8 m以下爲佳。 本發明之硏磨劑之回收方法係其特徵爲將在CMP工程 所使用之使用完的硏磨漿料，通水於孔道爲圓筒狀，有效 過濾部的長度爲0.8 m以下之分離膜，可將前述使用完的 硏磨漿料之硏磨劑濃度，濃縮成1 〇質量％以上之濃度者。 對於前述分離膜之中空部，係將前述使用完的硏磨漿料， 由叉流方式加以通水爲佳。另外，前述分離膜之內徑係 0.1mm以上0.8mm以下爲佳。另外，在前述分離膜之有效 過濾部的被處理水之循環流速係0.5〜2m/SeC爲佳。 可作爲具有於孔道爲圓筒狀之前段分離膜，將在CMP 工程所使用之使用完的硏磨漿料進行通水而濃縮前述使用 完的硏磨漿料之第1之過濾工程，和於有效過濾部之長度 爲0.8 m以下之後段分離膜，將前述第1之分離膜之濃縮水 進行通水而濃縮之第2之過濾工程，作爲前述前段分離膜 ，使用具有較前述後段分離膜爲長之有效過濾長度的分離 膜。在前述第1之過濾工程中，因依存於客戶工場之排水 -10- 201235090 之硏磨劑濃度之故而未特別加以限定，一般而言’過濾 0.02〜5質量％之使用完的硏磨漿料而濃縮至最大13質量％ ，更佳爲濃縮至9〜1〇質量％’而在前述第2之過濾工程中 ，過濾在前述第1之過濾工程所得到之1 3質量％以下之濃 縮水而濃縮至最大26質量％，更佳爲濃縮至20〜25質量％ 爲佳。另外，前述硏磨劑之回收方法係舞用上述之本發明 的硏磨劑之回收裝置爲佳。 [發明之效果] 如根據本發明之使用完的硏磨劑之回收裝置，由使用 有效過濾部之長度爲特定値以下之分離膜者，對於過濾面 之膠凝的堆積，或在被處理水出口側之硏磨劑之凝膠狀堆 積等不良情況變爲不易產生。因此，可至十數％程度以上 之硏磨劑濃度，濃縮漿料。另外，可將在CMP工程所使用 之後使用完的硏磨漿料，以較以往爲低之能量濃縮成高濃 度，作爲製品而可至利用可能之位準，回收濃縮硏磨劑爲 高濃度之漿料。另外，如此進行高濃度之濃縮，可抑制膜 內之壓力損失的增大，或分離膜之閉塞，可作爲抑制回收 率顯著下降之硏磨劑之回收裝置》 另外，在本發明之使用完的硏磨漿料之回收方法中， 未產生回收率顯著下降，而作爲製品而可至利用可能之位 準’回收濃縮硏磨劑爲高濃度之漿料。由此，可將使用於 CMP工程之新的漿料的使用量，削減60%以上。 -11 - 201235090 【實施方式】 以下，對於本發明之硏磨劑之回收裝置及硏磨劑之回 收方法詳細加以說明。 (第1實施形態） 圖1係顯示有關本發明之一實施形態之硏磨劑之回收 裝置之槪略構成圖。在本實施形態之硏磨劑之回收裝置1 係經由CMP工程而除去含於硏磨半導體之後之使用完的硏 磨漿料S (以下，顯示爲使用完的硏磨漿料S)之粗大粒子 的防護過濾器2，和收容防護過濾器2之處理水的處理容器 槽3，和具備過濾使用完的硏磨漿料S之分離膜41之膜分離 部4則沿著流路而加以依序設置。 然而，防護過濾器2係捕捉硏磨劑，或硏磨半導體晶 圓時之硏磨墊屑等發生凝結而產生之粒子徑大之固體不純 物之構成。防護過濾器2係如爲具有較硏磨劑粒子爲大之 孔徑的構成，並無特別加以限定而可使用。 防護過濾器2及處理容器槽3間係經由配管5所連接。 處理容器槽3及膜分離部4間係經由具備幫浦P1之配管6所 連接》然而，對於處理容器槽3係設置有成分濃度計C1。 對於膜分離部4係連接有透過水出口配管7，及具備開 關閥B 1之濃縮水出口配管8。濃縮水出口配管8係呈供給在 膜分離部4所得到之濃縮水供給至濃縮水回收容器槽9地加 以開口。 對於濃縮水出口配管8之開關閥B1的上流部與處理容 -12- 201235090 器槽3間，係設置有經由開關閥B 1之閉鎖及開關閥B2之開 放，將在膜分離部4所得到之濃縮水回流至處理容器槽3之 回流配管1 〇。 分離膜41係具有圓筒狀之孔道。於此孔道內部，或其 外側，由通過使用完的硏磨槳料S者’成爲除去使用完的 硏磨漿料S之過剩的水分而加以濃縮。 作爲具有圓筒狀之孔道的第1之分離膜41，例如可適 用中空系型，管狀型，或平膜型之分離膜。此等之中，中 空系型之分離膜係省空間且可得到大的膜面積之故，作爲 分離膜41而最佳適合使用。 分離膜4 1之有效過濾部之長度L係經由目的濃縮濃度 爲0.8m以下，理想爲〇.5m以下，更理想爲〇.3m以下。一般 而言，例如中空系型之分離膜的情況，當將高濃度之漿料 進行通水於分離膜時，在濃縮水通過其有效過濾部之過程 ，於中空系410之過濾面41 2上堆積有固體成分。更且，繼 續通水時，經由堆積於過濾面412上之固體成分而形成膠 凝層，其厚度則增大（參照圖2 )。分離膜4 1之過濾面4 1 2 上的膠凝層係其有效過濾長度越長而越容易加以形成。經 由膠凝層之形成，中空系4 1 0之有效內徑4 1 0 S則產生狹小 化’而有著壓力損失的增大，或膜的閉塞產生，硏磨劑之 回收效率顯著下降情況。另外，膠凝層或凝膠狀之堆積物 係由硏磨劑粒子加以形成之故，伴.隨著膠凝層之增大或凝 膠狀堆積物之產生，硏磨劑粒子之回收率則下降。 更且，如圖8所示’於中空系之被處理水出口側，硏 -13- 201235090 磨劑則堆積成凝膠狀，過濾處理的繼續則變爲困難。另外 ，對於過濾面的洗淨所需之藥品量或洗淨時間增加.，成爲 對於硏磨劑回收工程全體所需之成本增大的原因。 在本發明之硏磨劑之回收裝置1中，作爲分離膜41， 使用有效過濾部之長度L爲0.8m以下，理想爲0.5m以下， 更理想爲〇.3m以下之分離膜。對於使用如此之特定値以下 之有效過濾長度模組之情況，即使將高濃度之使用完的漿 料進行通水，亦不易產生篩孔堵塞。因此，抑制在過濾面 412上之膠凝層的成長同時，未產生有凝膠狀之堆積。 隨之，即使將高濃度的被處理水進行通水，亦可作爲 抑制在分離膜41之壓力損失的增大，或不易產生膜的閉塞 ，回收率之顯著下降之回收裝置1。 另外，如上述，於過濾面412上形成膠凝層時，亦有 硏磨劑粒子凝膠化之粗大粒子則從膠凝層剝離，混入於被 處理水中之情況。如此之粗大粒子則混入於回收後之硏磨 劑時，在CMP工程再利用時，在晶圓表面引起刮痕，成爲 使製品之產率下降的原因。 在本發明之硏磨劑之回收裝置1中，作爲分離膜41， 使用其有效過濾部之長度L爲上述範圍之分離膜。因此， 抑制在分離膜內部之膠凝層的形成，或經由凝膠狀物質之 堆積的粗大粒子之生成，極爲降低對於回收後之硏磨劑粒 子之粗大粒子的混入量。隨之，即使對於CMP工程再利用 ，亦幾乎未使晶圓表面之刮痕等產生，可高精確度地回收 硏磨可能之硏磨劑。 -14- 201235090 對於分離膜41之有效過濾部之長度L超過0.8m之情況 ，在分離膜41之過濾面412上，膠凝層的厚度容易增大， 而成爲容易產生經由有效內徑之狹小化的壓力損失之增大 ，或膜的閉塞。 分離膜41之有效過濾部之長度L係在上述的範圍內， 且爲0.2m以上爲佳。分離膜41之有效過濾部之長度L不足 0.2m時，設置於回收裝置1之分離膜41的模組支數則增加 ，設置適當之過濾處理裝置之情況則變爲困難。分離膜41 之有效過濾部之長度L係理想爲0.2〜0.3m。 分離膜41係亦可爲由有機材料所成之有機膜，而由無 機陶瓷所成之無機膜亦可。 作爲有機膜，係例如可最佳使用聚乙烯（PE ) ，4氟 化乙烯（PTFE)，聚偏二氟乙烯（PVDF )，聚丙烯（PP )，醋酸纖維素（CA)，聚丙稀睛（PAN)，聚醯亞胺（ PI)，聚颯（PS)及聚醚砸（PES)等》 另外，作爲無機膜，係可使用氧化鋁（Al2〇3 )，氧 化鉻（Zr〇2 )，氧化鈦（Ti02 )之陶瓷材料，或不鏽鋼（ SUS )，玻璃（SPG)等。此等之中，作爲分離膜41係可 最佳適合使用聚颯（PS)，聚醚砸（PES)。 分離膜41係如爲具有中空系型之形狀的構成，亦可爲 精密過濾膜，或額外過濾膜亦可。從最有效率回收回收後 之濃縮液中的硏磨劑粒子之觀點，分離膜4 1係可最佳適合 使用額外過濾膜》 分離膜41之分劃分子量係3,000〜30,000爲佳。當分 -15- 201235090 離膜41之分劃分子量不足3,0 00時，爲了將被處理水進行 通水於分離膜4 1而得到透過水，必須使對於分離膜4 1之供 給壓力上升。因此，能量效率降低之同時，有對於分離膜 41帶來損傷之虞。 另一方面，當分離膜41之分劃分子量超過3 0,000時， 硏磨劑粒子的一部分則通過分離膜4 1而移動至透過水側， 有無法有效率地回收硏磨劑粒子之虞。另外，此情況，經 由具有與分離膜41的孔徑略同徑之細微粒子，容易將分離 膜41的孔閉塞，而有產生篩孔堵塞之虞》分離膜41之分劃 分子量係6000〜10000爲更佳。 分離膜41爲中空系型分離膜或管狀分離膜之情況，各 中空系等之內徑係0.1 mm以上0.8mm以下爲佳。分離膜41 之各中空系等之內徑不足0.1 mm時，流動在膜的中空部之 被處理水之壓力損失則增大，得到適當之處理效率情況則 變爲困難。另外，此情況，膜面強度則下降，而有伴隨被 處理水之濃度上升而膜產生破損之虞。另一方面，分離膜 41之各中空系等之內徑超過0.8mm時，流動在膜的中空部 之被處理水之剪斷速度小之故，硏磨劑其他之不純物則容 易堆積於中空系內壁，而有使中空部閉塞之虞。另外，硏 磨劑之凝膠大量產生，而有濃縮液中之硏磨劑濃度下降之 虞。對於使剪斷速度上升，係必須加大設備，另外將消耗 許多能量之故而並不理想。更且，有著對於外壓而言之耐 壓性降低之虞。分離膜41之各中空系等之內徑係〇.3mm以 上0.8mm以下爲更佳。 -16 - 201235090 膜分離部4係亦可爲將被處理水通水於中空系4i〇內部 之內壓型之分離部，而將被處理水通水於中空系410之支 持層411之外側的外壓型之分離部亦可。膜分離部4係對於 作爲內壓型之分離部之情況，堆積於過濾面412上之固體 成分，則經由通水於中空系410內之被處理水的剪斷力加 以剝離，可抑制膠凝層之成長之故而爲理想。 由作爲如此之回收裝置1者，從透過水出口配管7所得 到之透過水係可回收加以再利用。具體而言，例如保持未 處理，或作爲對應於透過水之水質的處理之後，可作爲超 純水裝置之原水等而利用。另外，亦可作爲工場內之其他 的功用，例如生活用水，冷卻塔用水等而利用。 (第2實施形態） 圖3係顯示有關本發明之一實施形態之硏磨劑之回收 裝置之槪略構成圖。在本實施形態之硏磨劑之回收裝置11 係於經由CMP工程而除去含於硏磨半導體之後之使用完的 硏磨漿料S (以下，顯示爲使用完的硏磨漿料S)之粗大粒 子的防護過濾器12之後段’收容防護過濾器12之處理水的 前段處理容器槽13，具備過濾使用完的硏磨獎料s之前段 分離膜（以下，顯示爲第1之分離膜）141之前段膜分離部 (以下，顯示爲第1之膜分離部）1 4則沿著流路而加以依 序設置。 然而，防護過濾器12係捕捉硏磨劑’或硏磨半導體晶 圓時之硏磨墊屑等發生凝結而產生之粒子徑大之固體不純 -17- 201235090 物之構成。防護過濾器12係如爲具有較硏磨劑粒子之粒徑 爲大之孔徑的構成’並無特別加以限定而可使用。防護過 濾器1 2及前段處理容器槽1 3間係經由配管1 5所連接。前段 處理容器槽13及第1之膜分離部14間係經由具備幫浦P2之 配管16所連接。然而’對於前段處理容器槽13係設置有成 分濃度計C2。 對於第1之膜分離部14之後段’係依序加以設置收容 由第1之膜分離部14所分離之濃縮水（以下，有顯示爲第1 之濃縮水之情況）之後段處理谷器槽1 7 ’和具備過爐從後 段處理容器槽1 7所供給之第1之濃縮水的後段分離膜（以 下，顯示爲第2之分離膜）181之後段膜分離部（以下，顯 示爲第2之膜分離部）18，和回收由第2之膜分離部18所分 離之濃縮水（以下，有顯示爲第2之濃縮水之情況）之回 收容器槽19。然而，對於後段處理容器槽17係設置有成分 濃度計C3。 第1之膜分離部U及後段處理容器槽17間係經由具備 開關閥B3之配管20加以連接。後段處理容器槽17及第2之 膜分離部1 8間係經由具備幫浦P3之配管2 1所連接。 對於第1之膜分離部14係連接有第1透過水出口配管22 。另外，對於配管20之開關閥B3之前段與前段處理容器槽 13間，係設置有經由開關閥B3之閉鎖及開關閥B4之開放 ，將在第1之膜分離部1 4所得到之第1之濃縮水回流至前段 處理容器槽13之回流配管23。 對於第2之膜分離部18係連接有第2之透過水出口配管 -18- 201235090 24，及具備開關閥B5之濃縮水出口配管25。濃縮水出口配 管25係呈供給在第2之膜分離部18所得到之濃縮水供給至 回收容器槽1 9地加以開口。對於濃縮出口水配管25之開關 閥B5之上流部與後段處理容器槽17間，係設置有經由開關 閥B5之閉鎖及開關閥B6之開放，將在第2之膜分離部18所 得到之第2之濃縮水回流至後段處理容器槽1 7之回流配管 26。 第1之分離膜141，第2之分離膜181係具有圓筒狀之孔 道。於此孔道內部，或其外側，由通過使用完的硏磨漿料 S者，成爲除去使用完的硏磨漿料S之過剩的水分而加以濃 縮。作爲具有圓筒狀之孔道的第1之分離膜141，例如可適 用中空系型，管狀型，或平膜型之分離膜。此等之中，中 空系型之分離膜係省空間且可得到大的膜面積之故，作爲 第1之分離膜141，第2之分離膜181而最佳適合使用。 第2之分離膜181係過濾設置於前段之第1之分離膜141 之濃縮水而更加加以濃縮，提高其硏磨劑濃度之構成。第 2之分離膜181之有效過濾部之長度L2係爲0.8m以下，理想 爲0.5m以下，更理想爲0.3m以下。 作爲第2之分離膜181，由使用上述之有效過濾長度之 分離膜者，即使將高濃度之使用完的漿料進行通水’亦不 易產生膜的篩孔堵塞，抑制膠凝層之成長。因此’即使將 高濃度的被處理水進行通水’亦可作爲抑制在第2之分離 膜181之壓力損失的增大，或不易產生膜的閉塞，回收率 之顯著下降之回收裝置11。 -19- 201235090 對於第2之分離膜181之有效過濾部之長度L2超過0.8m 之情況，在第2之分離膜181之過濾面上，膠凝層的厚度容 易增大，而成爲容易產生經由有效內徑之狹小化的壓力損 失之增大，或膜的閉塞。第2之分離膜181之有效過濾部之 長度L2係從與在第1之實施形態之分離膜41同樣的理由， 特別理想爲〇 . 2〜〇 . 3 m。 第2之分離膜181之有效過濾部之長度L2係較第1之分 離膜1 4 1之有效過濾部之長度L 1爲短加以形成爲佳。即， 第1之分離膜141之有效過濾部之長度L1係較第2之分離膜 181之有效過濾部之長度L2爲長加以形成爲佳。 由此，在第1之分離膜141中，有效率地過濾處理由分 散媒體加以稀釋之低濃度之使用完的硏磨漿料S之同時， 而在第2之分離膜181中，將在第1之分離膜141所得到之第 1之濃縮水，更加地加以過濾處理。由此，作爲製品至可 再利用可能之位準，將硏磨劑粒子濃縮爲高濃度之漿料， 以低能量加以回收。 在近年中，在CMP工程所排出之使用完的硏磨漿料係 相當一曰之排出量有超過l〇〇〇m3之情況。因此，要求經由 更有效率之處理，除去、回收含於漿料的水之同時，回收 硏磨劑成分之技術。 在本實施形態中，如前述由作爲二段構成者’經由設 置於前段，膜面積大之第1之分離膜141，可大幅度地降低 被處理水之體積之同時，經由設置於後段之第2之分離膜 I 8 1，未有產生篩孔堵塞，而可將被處理水濃縮爲更高濃 -20- 201235090 度。因此，與第1之實施形態做比較，成爲可降低所使用 之模組之支數。 對於第2之分離膜181之有效過濾部之長度L2則與第1 之分離膜141之長度L1同等或超過此之情況，在第2之分離 膜181之內部，膠凝層的厚度容易增大，而成爲容易產生 經由有效內徑之狹小化的壓力損失之增大，或膜的閉塞。 第1之分離膜141之有效過瀘部之長度L1係無特別加以 限定，但考慮膜面積等〇.8〜1.5m爲佳。第1之分離膜141 之有效過濾部之長度L1不足0.8m時，有著設置於回收裝置 11之分離膜141之模組支數增大，以及設置面積變大，作 爲回收裝置而無法得到充分之效果之虞。 另一方面，第1之分離膜141之有效過濾部之長度L1超 過1.5m時，有著對於第1之分離膜141之設置高度產生有限 制，以及分離膜141之裝卸成爲困難之虞。第1之分離膜 141之有效過濾部之長度L1係更理想爲0.8〜1.5m。 第1之分離膜141係如爲具有圓筒狀之孔道之構成，亦 可爲精密過濾膜，而額外過濾膜亦可。可最佳適用效率佳 回收硏磨劑粒子（磨粒），另外將回收後之濃縮液中的硏 磨劑粒子之粒度保持爲一定，孔徑小，另外對於能量效率 佳之額外過濾膜。 另外，第2之分離膜181亦如爲具有中空系型之形狀的 構成，亦可爲精密過濾膜，或額外過濾膜亦可。從保持高 的回收後之濃縮液中的硏磨劑粒子之回收率的觀點，可最 佳適用額外過濾膜。 -21 - 201235090 第1之分離膜141及第2之分離膜181之分劃分子量係 3，000〜30,000爲佳。當第1之分離膜141及第2之分離膜 1 81之分劃分子量不足3,000時，爲了將被處理水進行通水 於分離膜而得到透過水，必須使對於分離膜之供給壓力上 升。因此，能量效率降低之同時，有對於分離膜帶來損傷 之虞。 另一方面，當第1之分離膜141及第2之分離膜181之分 劃分子量超過3 0,000時，硏磨劑粒子的一部分則通過第1 之分離膜141而移動至透過水側，有硏磨劑粒子之回收效 率下降之虞。另外，此情況，經由具有與分離膜141的孔 徑略同徑之細微粒子，容易將分離膜141及第2之分離膜 1 8 1的孔閉塞，而有產生篩孔堵塞之虞。 第1之分離膜141及第2之分離膜181爲中空系型分離膜 或管狀型分離膜之情況，其內徑係0.1mm以上0.8mm以下 爲佳。第1之分離膜141之各中空系等之內徑不足0.1 mm時 ，流動在膜的中空部之被處理水之壓力損失則增大，得到 適當之處理效率情況則變爲困難之同時，分離膜141之膜 面強度下降，有伴隨被處理水之濃度上升而膜產生破損之 虞。另一方面，第1之分離膜141之各中空系等之內徑 0.8mm以上時，有流動在膜的中空部之被處理水之剪斷速 度小，硏磨劑或其他之不純物則容易堆積於中空部之內壁 ，以及使中空部閉塞，硏磨劑粒子發生凝結之凝膠則大量 產生，回收後之濃縮液中之硏磨劑濃度下降之虞。第1之 分離膜141及第2之分離膜181爲中空系等內徑係〇.3mm以 -22- 201235090 上0.8mm以下爲更佳。 第1之分離膜141及第2之分離膜181係亦可爲由有機材 料所成之有機膜，而由無機陶瓷所成之無機膜亦可。作爲 有機膜，係例如可最佳使用聚乙烯（PE ) ，4氟化乙烧（ PTFE)，聚偏二氟乙烯（PVDF )，聚丙烯（PP)，醋酸 纖維素（CA)，聚丙稀睛（PAN )，聚醯亞胺（PI)，聚 颯（PS )及聚醚楓（PES )等。 另外，作爲無機膜，係可使用氧化鋁（ai2o3 )，氧 化鉻（Zr〇2 )，氧化鈦（Ti02 )之陶瓷材料，或不鏽鋼（ SUS )，玻璃（SPG )等。此等之中，作爲第1之分離膜 141及第2之分離膜181係可最佳適合使用聚颯（PS)，聚 醚楓（PES )。 第1之分離膜141及第2之分離膜181係爲中空系型之分 離膜之情況，係亦可爲將被處理水通水於中空系內部之內 壓型的分離部，而將被處理水通水於中空系之支持層的外 側之外壓型的分離部亦可。對於作爲內壓型之分離部之情 況，堆積於過濾面上之固體成分，則經由通水於中空系內 之被處理水的剪斷力加以剝離，可抑制膠凝層之成長之故 而爲理想。 在如此之回收裝置11中，經由第1之分離膜141，可將 漿料的稀薄溶液濃縮至某種程度之故，可有效率地濃縮大 量之CMP排水。特別在製造規模大之半導體工場中，相當 1曰排水量由成爲1000噸以上之情況，但由設置第1之分離 膜141者，可將如此之大量的排水降低爲約1/10〜1/500的 -23- 201235090 量。隨之，與未設置第1之分離膜141之第1之實施形態做 比較，可降低作爲全體而設置之模組支數° 以上，對於本發明之硏磨劑之回收裝置11 ’以舉過其 —例說明過，但在不違反本發明之內容之限度’可適宜變 更其構成。 接著，依據圖3，對於使用本發明之硏磨劑之回收裝 置11之硏磨劑之回收方法加以說明。然而，在本實施形態 中，作爲第1之分離膜141，第2之分離膜181，均對於使用 具備中空系型之額外過濾膜之硏磨劑之回收裝置11的情況 加以說明。第1之分離膜141係如爲具有圓筒狀之孔道之構 成，不爲中空系型的分離膜亦可.，而亦可爲管狀型或平膜 型之構成。 處理對象之使用完的硏磨漿料S係如爲含有在CMP工 程（化學性機械硏磨工程）所使用之後的硏磨劑之工程， 並無特別加以限定。作爲如此之硏磨劑粒子係例如可舉出 矽素粒子，铈粒子等。作爲硏磨劑粒子係通常，最佳使用 平均粒子徑爲〇.〇1〜Ιμηι之構成。硏磨劑之平均粒子徑係 經由CMP工程加以適宜選定，但例如爲0.04〜0.4μιη。 首先，在CMP工程所使用之使用完的硏磨漿料S係經 由配管15而供給至防護過濾器12。使用完的硏磨漿料S係 在通過防護過濾器12之過程而除去粒徑數十μηι以上之粗 大粒子之後，儲存於前段處理容器槽13。 使用完的硏磨漿料S之在未處理階段的硏磨劑粒子的 濃度係依存於客戶工場之故而未加以特別限定。在CMP工 -24- 201235090 程之使用完的硏磨漿料s的硏磨劑濃度係通常爲〇· 02〜5質 量％。 儲存於前段處理容器槽13之使用完的硏磨漿料S係在 關閉開關閥B3，開啓開關閥B4之狀態’經由幫浦P2歷經 配管16而加壓供給至具備第1之分離膜141之第1之膜分離 部14。使用完的硏磨漿料S係在通過防護過濾器12之過程 而除去粒徑數十μπι以上之粗大粒子之後，以叉流方式加 以通水至第1之分離膜141之各中空系內部’在通過其有效 過濾部之過程，透過過剩的水分，加以濃縮（第1之過濾 工程）。此時，使用完的硏磨發料S之分散媒體等係通過 分離膜141而流出於透過水出口配管22’使用完的硏磨漿 料S內之硏磨劑粒子係殘留於第1之分離膜1 4 1之濃縮水的 第1之濃縮水側。 第1之濃縮水係通過回流配管23而回流至前段處理容 器槽13。在特定時間繼續此工程之後’在以成分濃度計C2 所計測之前段處理容器槽13內之儲存水的硏磨劑之濃度成 爲最大13質量％ ’更佳爲9〜10質量％之階段’開啓開關閥 Β 3，關閉開關閥Β 4，其一部分則歷經配管2 0而供給至後 段處理容器槽1 7。 通過第1之分離膜141之有效過濾部’被處理水（使用 完的硏磨漿料S及第1之濃縮水）之流速爲〇·5〜2m/sec爲佳 。在第1之分離膜141之有效過濾部’被處理水（使用完的 硏磨漿料S及第1之濃縮水）之流速不足〇·5 m/see時，容易 於分離膜141之過濾面附著有硏磨劑粒子’而有透過水量 -25- 201235090 下降者。此情況，必須使分離膜141設置支數增加，回收 裝置11之製造成本變高。另一方面，在第1之分離膜141之 有效過濾部之被處理水的流速超過2.0 m/sec時，接觸於膜 面之液量變爲過剩，有產生發熱者。此情況，分離膜141 ’濃縮液則同時受到經由熱的損傷，而有產生劣化之虞。 另外’對於使分離膜141之被處理水的流速提昇，有必要 增大各配管或閥等之尺寸，回收裝置11之製造成本則變高 °通過第1之分離膜141之有效過濾部之被處理水的流速係 更理想爲 0.55~1.5m/sec。 儲存於後段處理容器槽1 7之第1之濃縮水係在關閉開 關閥B5，開啓開關閥B6之狀態，經由幫浦P3歷經配管21 而加壓供給至具備第2之分離膜181之第2之膜分離部18。 第2之分離膜181係較第1之分離.膜141之有效過濾長度L1爲 短，且具有〇.8m以下，理想爲0.5m以下，更理想爲0.3m以 下之有效過濾長度L2。第2之分離膜181係於各中空系之中 空部，以叉流方式將第1之濃縮水加以通水。第1之濃縮水 係在通過中空系之有效過濾部的過程，透過過剩的水分， 加以濃縮（第2之過濾工程）。此時，第1之濃縮水之分散 媒體等係通過分離膜181而流出於透過水出口配管24，含 於第1之濃縮水之硏磨劑粒子係殘留於第2之分離膜181之 濃縮水的第2之濃縮水側.。 通過第2之分離膜181之有效過濾部，被處理水（第1 之濃縮水）之流速爲0.5〜2m/sec爲佳。在第2之分離膜1 81 之有效過濾部，被處理水之流速不足0.5 m/sec時，容易於 -26- 201235090 分離膜181之過濾面附著有硏磨劑粒子，而容易產生膜的 閉塞。另一方面，在第2之分離膜181之有效過濾部之被處 理水的流速超過2 m/sec時，對於硏磨劑粒子加上過剩量 之能量，而有此粒子則發生凝結而形成粗大粒子。當混入 粗大粒子於回收後之硏磨劑時，對於CMP工程進行再利用 使用時，於晶圓等之表面產生刮痕，而有使製品之產率下 降者。另外，當如此之粗大粒子產生時，於分離膜之過濾 面形成有膠凝層，而有洗淨時間或藥品之使用量增加之虞 。通過第2之分離膜181之有效過濾部之被處理水的流速係 更理想爲〇.6~lm/sec。 在特定時間繼續上述之處理工程之後，在以成分濃度 計C3所計測之後段處理容器槽17內之儲存水的硏磨劑之濃 度成爲目標濃度之階段，開啓開關閥B5，關閉開關閥B6 ，其一部分則歷經配管25而供給至回收容器槽1 9。歷經配 管25而供給至回收容器槽19時之後段處理容器槽17內之儲 存水的濃度係理想爲10質量％以上，且最大26質量％，更 理想爲20〜25質量％。 在第2之分離膜181之過濾面，被處理水之壓力損失係 O.IMPa以下爲佳，而0.08MPa以下爲更佳。 在本發明之硏磨劑之回收方法中，使用具有較第1之 有效過濾長度爲短之有效過濾長度之第2之分離膜181之故 ，抑制在第2之分離膜之過濾面的壓力損失之增大，或膜 的閉塞同時，作爲製品至可使用之位準，可有效率回收硏 磨劑粒子濃縮成高濃度之使用完的硏磨漿料S。 -27- 201235090 然而，在本實施形態中，顯示過第1之過濾工程，第2 之過濾工程同時，將被處理水通水至中空系之中空部，以 內壓型之方式進行過濾處理之方法，但本發明未必限定於 如此之形態。例如，作爲將被處理水通水至中空系之外側 ，以外壓型之方式進行過濾處理亦可。 由第1透過水出口配管22及第2透過水出口配管24所得 到的透過水係可回收進行再利用。例如保持未處理，或作 爲對應於透過水之水質的處理之後，可作爲超純水裝置之 原水等而利用。另外，亦可作爲工場內之其他的功用，例 如生活用水，冷卻塔用水等而利用。 [實施例] 以下，經由實施例及比較例，詳細說明本發明。 (實施例1 ) 使用圖1所示之硏磨劑之回收裝置1而進行在CMP工程 之使用完的漿料之過濾處理。 作爲在圖1之幫浦P1，係使用levitro pump「LEV300 」（股份有限公司IWAKI製、商品名），作爲膜分離部4 ，係使用中空系型UF膜模組「FB02-VC-FUST6 5 3」（ Daicen Membrane Systems股份有限公司製、商品名）。 作爲處理容器槽3，濃縮水回收容器槽9，係使用濃縮容器 槽（PVC製）。中空系型UF膜模組「FB02-VC-FUST653」 係分劃分子量；6000，中空系內徑；0_5mm，膜面積： -28- 201235090 0.5m2，有效過濾長度；0.26m。 首先，將硏磨劑濃度約1質量％ (pH: 9.8)之使用完 的硏磨漿料溶液’從配管5歷經防護過濾器2而供給至處理 容器槽3。接著，關閉開關閥B1，開啓開關閥B2，將處理 容器槽3內之使用完的硏磨漿料進行通水至膜分離部4。使 用完的漿料之各配管內之循環流量係作爲8.1L/min,中空 系膜41內之線速係作爲0.5 5m/sec。另外，在中空系膜41 ，使用完的硏磨漿料流入口附近之壓力呈成爲0.2MP a地， 調製幫浦PI ( levitro pump)之葉輪旋轉數，及膜分離部4 之後段的開關閥B2之開關度。在此狀態進行通水處理，測 定以成分濃度計C 1所計測之處理容器槽3內之硏磨劑之濃 度，及從透過水出口配管所排出之透過水量（flux )。 (實施例2 ) 作爲膜分離部4，除使用中空系型UF膜模組「 M8 1S6000 1N」（SPECTRUM公司製、商品名）以外，與 實施例1同樣作爲進行使用完的硏磨漿料之通水處理，與 實施例1同樣作爲測定處理容器槽3內之硏磨劑濃度。 然而，中空系型UF膜模組「M81S6000 1N」係中空系 內徑；0.5mm，有效過濾長度；〇.46m。 (實施例3 ) 作爲膜分離部4，除使用中空系型UF膜模組「 KM1S60001N」（SPECTRUM公司製、商品名）以外，與 -29- 201235090 實施例1同樣作爲進行使用完的硏磨漿料之通水處理，與 實施例1同樣作爲測定處理容器槽3內之硏磨劑濃度。 然而’中空系型UF膜模組「KM1S6000 1 N」係中空系 內徑：〇.5mm，有效過濾長度；〇.63m。 (比較例1 ) 作爲膜分離部4，除使用中空系型UF膜模組「 KM1S30001N」 （SPECTRUM公司製、商品名）以外，與 實施例1同樣作爲進行使用完的硏磨漿料之通水處理，與 實施例1同樣作爲測定處理容器槽3內之硏磨劑濃度。然而 ，中空系型UF膜模組「KM1S3000 1N J係中空系內徑； 0.5mm，有效過濾長度；〇.81m。 (比較例2 ) 作爲膜分離部4，除使用中空系型UF膜模組「AMK-VC-FUST653 j (Daicen Membrane Systems股份有限公司 製、商品名）以外，與實施例1同樣作爲進行使用完的硏 磨漿料之通水處理，與實施例1同樣作爲測定處理容器槽3 內之硏磨劑濃度。然而，中空系型UF膜模組「amk-vc-fustgss 」 係中空系內徑；〇.5mm，有效過濾長度；1.0m ，膜面積；1.5m2。 在實施例1及比較例2中，將以成分濃度計c 1所計測之 處理容器槽3內之硏磨劑濃度與從透過水排出口配管7所排 出之透過水量（flux)之關係，示於圖4。 -30- 201235090 然而，在圖4中，虛線係顯示來自在實施例1之透過水 出配管7之透過水量，實線係顯示來自在比較例2之透過出 口配管7之透過水量。另外，於表1顯不，與實施例1〜3, 比較例1〜2之各中空系分離膜4丨之中空系內徑’膜面積， 有效過濾長度，材質同時’在通水開始時點之被處理水研 磨劑濃度，及濃縮處理變爲不能之時點之被處理水硏磨劑 濃度（濃縮可能最大濃度）° [表1] 中空系 內徑 [mm] 膜面積 [m2] 有效過 濾長度 [m] 材質 被處理水硏 磨劑濃度 (通水開始時點) [質量％] 被處理水硏 磨劑濃度 (過濾處理結束時點） [質量％] 實施例1 0.5 0.50 0.26 PES1) 1 25 實施例2 0.5 6.6 0.46 PS2) 1 22 實施例3 0.5 8.2 0.63 PS 1 20 比較例1 0.5 11.2 0.81 PS 1 17 比較例2 0.5 1.5 1.0 PES 1 13 1 )聚醚楓 2 )聚楓 從表1明確了解到’在分離膜41之有效過濾長度爲 0.8m以下之實施例1~3的回收裝置中，在過濾處理結束時 點，可得到具有2 〇質量％以上之高濃度的硏磨劑濃度的處 理水，認爲隨著有效過濾長度變短’濃縮可能最大濃度增 大。另一方面，在具有超過〇.8m之有效過濾長度的比較例 1之回收裝置中，濃縮可能最大濃度成爲不足20質量％， -31 - 201235090 認爲在高濃度範圍容易產生篩孔堵塞。 另外，如圖4所示，作爲膜分離部4，在使用具有超過 0.8m之有效過濾長度的分離膜41之比較例2之回收裝置中 ，在被處理水的Si濃度超過13質量％之時點，透過水量（ flux )急遽減少，進行此等以上之過濾處理則爲困難。另 一方面，作爲膜分離部4，在使用具有〇.8m以下之有效過 濾長度的分離膜41之實施例1的回收裝置中，即使被處理 水的濃度超過20質量％，未產生有透過水量之急遽的減少 ，而被處理水即使成爲高濃度，亦可安定進行過濾處理。 從以上之結果，作爲膜分離部4，使用有效過濾長度 爲0.8m以下之分離膜41的情況，認爲將從CMP工程所排出 之低濃度的使用完的漿料，可安定濃縮至高濃度範圍。 含有二氧化矽粒子等之硏磨劑粒子的排液係從遵守排 水基準的必要性，從以往進行固液分離者。但即使對於固 液分離使用額外過濾膜，作爲固體成分之濃縮係界限爲數 %程度。在磨粒成分之濃度爲數％程度中，作爲硏磨漿料 而對於CMP工程進行再利用之情況係困難之故，固體成分 係一般而言，作爲產業廢棄物加以廢棄處理。 在本發明中，如在實施例1〜3所示地，將來自CMP工 程之排水的硏磨劑濃度，作爲製品而可濃縮處理至使用可 能之25 %程度之濃度之故，可將所回收之濃縮液再次使用 於CMP工程，可得到高再利用效率。 接著，使在實施例1使用之硏磨劑之回收裝置1，在膜 分離部4之被處理水入口的壓力係作爲與實施例1相同，使 -32- 201235090 分離膜之壓力損失變化，進行實施例4〜5，比較例3〜6。 (實施例4 ) 將中空系膜41內之線速作爲0.6m/sec，除此之外的條 件係與實施例1相同作爲，將使用完的硏磨漿料通水至回 收裝置1，進行過濾處理。進行80分鐘此處理之後，開啓 開關閥B1，關閉開關閥B2，將膜分離部4之濃縮水，從濃 縮水出口配管8回收至濃縮水回收容器槽9。 (實施例5 ) 除變更以下的點以外係與實施例2相同作爲進行過濾 處理，回收膜分離部4之濃縮水。作爲膜分離部4，取代中 空系型UF膜模組「FB02-VC-FUST653」，使用中空系型 UF膜模組「SLP-1053」 （Asahi Kasei股份有限公司製、 商品名，中空系內徑：1.4mm，分劃分子量：10000 膜 面積：0.12 m2，有效過濾長度：0.20 m，膜材質：聚楓） 〇 將供給至處理容器槽3之使用完的硏磨漿料作爲硏磨 劑濃度約0 · 8質量％ ( pH : 1 0.5 )，將各配管內之使用完的 漿料的循環流量作爲9.OL/min，將在中空系膜41之使用完 的硏磨漿料流入口附近的壓力作爲0.2MPa，將中空系膜41 內之線速作爲0.69m/sec。 (比較例3 ) -33- 201235090 除變更以下的點以外係與實施例2相同作爲進行過濾 處理’回收膜分離部4之濃縮水。作爲膜分離部4，取代中 空系型UF膜模組「FB02-VC-FUST653」，使用中空系型 UF 膜模組「AMK-VC-FUS0181」（Daicen Membrane Systems股份有限公司製、商品名，中空系內徑：〇 8 mm ’分劃分子量：10000 膜面積：0.5 m2，有效過濾長度 :1m，膜材質：PES) ’將中空系膜41內之線速作爲0.55 m/sec ° (比較例4 ) 除變更以下的點以外係與實施例2相同作爲進行過濾 處理，回收膜分離部4之濃‘水。作爲膜分離部4，取代中 空系型UF膜模組「FB02-VC-FUST653」，使用中空系型 UF 膜模組「AMK-VC-FUS03C1」（Daicen Membrane Systems股份有限公司製、商品名，中空系內徑：1.2 mm ，分劃分子量：30000 膜面積：0.3 m2，有效過濾長度 :1 m，膜材質：PES)，將中空系膜41內之線速作爲0.85 m/sec ° (比較例5 ) 除變更以下的點以外係與實施例2相同作爲進行過濾 處理，回收膜分離部4之濃縮水。作爲膜分離部4，取代中 空系型UF膜模組「FB02-VC-FUST653」，使用「AMK-VC-FUS03C1」 （Daicen Membrane Systems股份有限公司 -34- 201235090 製、商品名，中空系內徑：ϊ·2 mm，分劃分子量：30000 膜面積：〇.3m2，有效過濾長度：1m，膜材質：PES)， 將中空系膜41內之線速作爲1·8 m/sec。 (比較例6 ) 除變更以下的點以外係與實施例2相同條件進行過濾 處理，回收膜分離部4之濃縮水。作爲膜分離部4’取代中 空系型UF膜模組「FB02-VC-FUST65 3」’使用「AMK-VC-FUST653」 （Daicen Membrane Systems股份有限公司 製、商品名，中空系內徑·· 〇.5mm’分劃分子量：6000 膜面積：1.5m2，有效過濾長度：1 m，膜材質：PES)。 中空系膜4 1內之線速係作爲與實施例2相同。 對於實施例4~5及比較例3〜6，將回收至濃縮水回收容 器槽9內之濃縮水的硏磨劑濃度，及硏磨劑的回收率示於 表2。另外，實施例4〜5及比較例3~6之中空系膜41內之線 速，中空系內徑，及從透過水的排出量所算出之濃縮液中 的硏磨劑濃度値，合倂示於表2。 -35- 201235090 [表2] 有效過 濾長度 Μ 中空系 內徑 [mm] 中空系膜 內線速 [m/sec] 濃縮液硏 磨劑濃度 (計算値） [質量％] 濃縮液硏磨 劑濃度 (測定簡 [質量％] 回收率 [%] 實施例4 0.26 0.50 0.60 26 25 98 實施例5 0.2 1.4 0.69 25 22 88 比較例3 1.0 0.80 0.55 17 13 76 比較例4 1.0 1.2 0.85 22 13 61 比較例5 1.0 1.2 1.8 22 13 60 比較例6 1.0 0.50 0.60 17 13 79 從表2明確了解到，在使用有效過濾長度爲0.8 m以下 ，分離膜之內徑爲0.1 mm以上0.8mm以下之分離膜的實施 例4中，回收後之濃縮液的硏磨劑濃度爲超過25質量％， 確認可得到更高的回收率。另外，與實施例4作比較，在 減短有效過濾長度之同時，增大中空系內徑而使壓力損失 降低之實施例5中，雖至比較高濃度之範圍可得到特定量 以上之透過水，但無法濃縮處理爲25質量％以上。另外， 含於回收後之濃縮液的硏磨劑濃度係低於從透過水量所算 出之硏磨劑濃度（計算値），確認到伴隨中空系內徑（纖 維徑）之增大，而硏磨劑之回收率產生若干下降。此係於 中空系內部附著磨粒成分（硏磨劑粒子）而形成膠凝層’ 認爲有效內徑產生狹小化者。 另一方面，在具有較〇.8m爲長之有效過濾長度，且中 空系內徑爲〇.l~〇.8mm2範圍的比較例3’ 6中，硏磨劑之 回收率係成爲76%附近，含於回收後之濃縮液之硏磨劑濃 -36- 201235090 度係低於從透過水量所算出之硏磨劑濃度（理論値）。另 外，在使中空系的內徑增大爲1.2.mm之比較例4，5中，硏 磨劑之回收率變爲更低。此係在中空系內部附著磨粒成分 (硏磨劑粒子）而形成膠凝層，認爲有效內徑產生狹小化 者。 . (比較例7 ) 於在圖1所示之回收裝置1，作爲膜分離部4而設置額 外過濾膜「MLE-7101H」（股份有限公司kuraray製，商 品名’有效過爐長度：1 m’中空系內徑：1.2mm，分劃 分子量：13000，膜材質：聚楓），進行過濾處理。過濾 處理係以內壓型之叉流方式進行。分離膜係從含於濃縮液 之硏磨劑濃度成爲14質量％的階段緩緩地產生閉塞。之後 ，提升幫浦的輸出，提高對於被處理水而言之壓力，繼續 過濾處理，但在被處理水之Si濃度成爲19質量％的階段， 濃縮處理成爲不可能。於圖6，顯示在無法進行過濾處理 之時點的膜分離部4入口之狀態，於圖7，擴大顯示圖6之 一部分，於圖8，顯示在同時點之膜分離部4出口之狀態。 如在圖8所示，對於在濃縮處理成爲困難之時點的膜 分離部，係於被處理水之通水方向的後段（膜分離部4的 出口），硏磨劑發生凝結之凝膠狀的粗大粒子則形成爲一 條。由此，分離膜41之中空部產生閉塞而濃縮處理之繼續 變爲困難》 -37- 201235090 (實施例6 ) 使用圖3所示之硏磨劑之回收裝置Π而進行在CMP工 程之使用完的漿料之過濾處理。 作爲在圖3之幫浦P2及P3係使用levitro pump「 LEV3 00」（股份有限公司IWAKI製、商品名）’作爲膜分 離部14係使用中空系型UF膜模組「AMK-VC-FUST65 3」（ Daicen Membrane Systems股份有限公司製、商品名）， 另外，作爲第2之膜分離部18係使用中空系型UF膜間模組 「FB02-VC-FUST653」(Daicen Membrane Systems 股份 有限公司製、商品名）。另外，作爲處理容器槽13及後段 處理容器槽17係使用處理容器槽（PE製），作爲濃縮水回 收容器槽19係使用濃縮容器槽（PVC製）。 第1之膜分離部14之中空系型UF膜模組「AMK-VC-FUST653」係分劃分子量：6000，中空系內徑：〇.5mm， 膜面積：1.5 m2，有效過濾長度：1 m，而第2之膜分離部 18之中空系型UF膜模組「FB02-VC-FUST653」係分劃分 子量：6000，中空系內徑：〇.5mm，膜面積：〇.5m2，有效 過爐長度：0.26 m。 首先’將硏磨劑濃度約1質量％ (pH: 9.8)之使用完 的硏磨漿料溶液’從配管15歷經防護過濾器12而供給2 00L 至處理容器槽13。接著’關閉開關閥B3，開啓開關閥B4 ’將處理容器槽13內之使用完的硏磨漿料進行通水至第1 之膜分離部14。使用完的漿料之各配管內之循環流量係作 爲8.0L/min’中空系膜141內之線速係作爲〇7m/sec。另外 -38- 201235090 ’在中空系膜141’使用完的硏磨黎料流入口附近之壓力 呈成爲〇.2MPa地’調製幫浦P2 ( levitro pump)之葉輪旋 轉數’及膜分離部14之後段的開關閥B4之開關度。 在此狀態進行通水處理，測定以成分濃度計C2所計測 之處理容器槽3內之硏磨劑之濃度至成爲.9質量％，從透過 水出口配管22所排出之透過水量（fiux )。此時之處理容 器槽13內之使用完的硏磨漿料係約22L。 接著，關閉開關閥B4，開啓開關閥B3，將處理容器 槽13內之使用完的硏磨漿料全量供給至後段處理容器槽17 。接著，關閉開關閥B5，開啓開關閥B6，將後段處理容 器槽17內之使用完的硏磨漿料進行通水至第2之膜分離部 18。使用完的漿料之各配管內之循環流量係作爲8. OL/min ，中空系膜181內之線速係作爲〇.7m/sec。另外，在中空 系膜181，使用完的硏磨漿料流入口附近之壓力呈成爲 0.2MPa地，調製幫浦P3 ( levitro pump )之葉輪旋轉數， 及膜分離部18之後段的開關閥B6之開關度。 在此狀態進行通水處理，測定以成分濃度計C3所計測 之處理容器槽3內之硏磨劑之濃度至成爲25質量％ ’從透 過水出口配管所排出之透過水量（flux )。 在實施例6中，將以成分濃度計C2所計測之處理容器 槽13內之硏磨劑濃度與從第1透過水排出配管22所排出之 透過水量（flux )之關係，及以成分濃度計C3所計測之處 理容器槽17內之硏磨劑濃度與從第2透過水排出配管24所 排出之透過水量（flux )之關係，示於圖5。然而’在圖5 -39- 201235090 中，實線係顯示從第1透過水排出配管22所排出之第1之膜 分離部14的透過水，虛線係顯示從第2透過水排出配管24 所排出之第2之膜分離部18的透過水。 依據實施例1之計測資料（圖4 )，實施例6之計測資 料（圖5)，設計製作實施例1之硏磨劑之回收裝置1(第1 實施形態），及實施例6之硏磨劑之回收裝置11 (第2實施 形態）。在第2實施形態之硏磨劑之回收裝置1 1中，與第1 實施形態之硏磨劑之回收裝置1作比較，可減少87%中空 系型UF膜模組之使用支數而製作。其結果，可得到作爲 回收裝置全體之配管構成之簡素化，設置面積之縮小化及 成本削減的效果。 【圖式簡單說明】 [圖1]顯示有關本發明之一實施形態之硏磨劑之回收 裝置之槪略構成圖。 [圖2]擴大構成分離膜41之一的中空系之剖面而顯示 的圖》 [圖3]顯示有關本發明之一實施形態之硏磨劑之回收 裝置之槪略構成圖。 [圖4]顯示處理容器槽內之硏磨劑濃度，和從透過水 排出配管所排出之透過水量（flux )之關係圖。 [圖5]顯示在圖3之回收裝置，處理容器槽13內之硏磨 劑濃度與從第1透過水排出配管22所排出之透過水量（ flux )之關係，及處理容器槽17內之硏磨劑濃度與從第2 -40- 201235090 透過水排出配管24所排出之透過水量 [圖6]顯示在分離膜閉塞時點之f 的照片。 [圖7]圖6之擴大照片。 [圖8]顯示在分離膜閉塞時點之f 的照片。 【主要元件符號說明】 1、1 1 :硏磨劑之回收裝置 3 :處理容器槽 41 :分離膜 4 1 0S :有效內徑 4 1 2 :過瀘面 7 :透過水出口配管 9:濃縮水回收容器槽 1 3 :前段處理容器槽 141 :第1之分離膜 15〜 1 7 :後段處理容器槽 181 :第2之分離膜 22:第1透過水出口配管 24:第2透過水出口配管 25: 26 :回流配管 C 1~C3 :成分濃度計 (flux)之關係圖。 i分離部入口之狀態 分離部出口之狀態 2、12 :防護過濾器 4 :膜分離部 410 :中空系 41 1 :支持層 5~6 :配管 8 :濃縮水出口配管 1 0 :回流配管 1 4 :第1之膜分離部 1 6、20〜2 1 :配管 U :第2之膜分離部 1 9 :回收容器槽 2 3 :回流配管 濃縮水出口配管 p 1 ~P 3 :幫浦 開關閥 -41 -201235090 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method and a recovery device for a honing agent, and more particularly to a method for recovering a honing agent capable of concentrating a used honing slurry into a high concentration And the use of this recycling device. [Prior Art] An insulating film formed on a semiconductor wafer, a film surface of a metal thin film or the like is required to have a flat surface having a high height. In order to cope with this requirement, CMP is performed in which the honing slurry is interposed between the honing member and the semiconductor wafer which are present in the honing pad or the like (Chemical Mechanical Polishing) & As a honing agent used in CMP, it is used as a cerium oxide fine particle having a good dispersibility and a uniform particle diameter, or a sirolimus fiber having a high honing speed, a high hardness, and a stable alumina. These honing agents are provided as a slurry having a specific particle diameter and a concentration of particles dispersed in water, which is supplied by the manufacturer. The slurry is used in each site to be diluted to a specific concentration when supplied to the CMP machine. Usually, in addition to the honing agent, a pH adjuster such as potassium hydroxide, ammonia, an organic acid or an amine, a dispersing agent such as a surfactant, hydrogen peroxide, and iodic acid are added in advance to the slurry. An oxidizing agent such as potassium or iron (III) nitrate. Alternatively, these ingredients are additionally added to the slurry during honing. These honing slurries are ideal for recycling from the point of view of the high amount of use and high cost, and the reduction of the amount of waste in the production of -5-201235090. However, the honing process drainage is diluted by most of the washing water, and the concentration of the honing agent is lowered. In addition, the honing engineering drainage system is mixed with a semiconductor wafer or a film material, a honing pad, a fine particle of a honing agent, or a solid impurity having a large particle diameter generated by condensation of a honing agent. Therefore, 'the drainage of such a honing project is used, when no treatment is used as a honing agent, the honing speed is lowered by the decrease in the concentration of the honing agent, and the scratch is formed on the surface of the wafer. The yield is reduced. In response to the re-use, it is necessary to remove the impurities such as the coarse solids from the honing water, and to carry out the concentration treatment, and to adjust the honing slurry of the specific composition. In the past, various technologies have been tried for the drainage treatment of CMP projects. For example, it is proposed to drain the CMP project, pass the water through a separation membrane such as a precision filtration membrane, an additional filtration membrane, and the like, and add a chemical or ultrapure water to prepare a concentration of the honing agent or the dispersing agent as a honing agent. The method of reusing the slurry. For example, in the first membrane element, the membrane concentration of the circulating liquid is maintained at a specific level, and the membrane is separated, and a part of the membrane element is extracted, and the second membrane is removed. A membrane treatment method for CMP drainage in which the element is further subjected to membrane separation. Further, Patent Document 2 discloses a method for separating a slurry-like honing liquid for a semiconductor having a desired particle diameter and a condensate for removing a fine particle from which a fine particle is condensed and having a large diameter. In Patent Document 2, the fine particles are removed by the additional filtration membrane 1 m of the first work 201235090, and the coarse particles which are the cause of the honing are removed by the second filtration filtration membrane 2m. Further, Patent Document 3 discloses that the pulverizer waste liquid of the CMP project is concentrated to a specific gravity of 0% by using a filter for concentration such as an additional filter membrane. 90 times ~ 0. After 96 times (one concentration project), the concentrate is more concentrated to 0% of the original solution. 9 9 times ~ 1. 0 1 times (secondary concentration engineering), and then using the method of honing agent. Patent Document 4 discloses a recovery device for a honing agent which reduces the amount of water discharged into the membrane separation means or the amount of dispersion in the drainage, and suppresses clogging of the screen at the early stage of the membrane. In Patent Document 4, the concentrated liquid concentrated by the membrane separation means of the first stage of the preceding stage is introduced into the second membrane separation means of the latter stage, and the coarse solid matter is removed by the second membrane separation means. In the hollow type separation membrane used in the above examples, an additional filtration membrane is widely used. The hollow type separation membrane is a module which is used to suppress the effective filtration length of the membrane, and is excellent in cost. Generally, a filtration length of lm is widely used. On the other hand, in the hollow type separation membrane, as the water to be treated becomes a high concentration, the solid component is deposited as a gel on the inner wall, and then the thickness of the gel is increased. Therefore, the effective inner diameter of the film is narrowed, and there is an increase in pressure loss, and a clogging of the film is produced, and the recovery rate of the honing agent is remarkably lowered. In particular, in the case of the treatment of the discharged water of the CMP project, when the concentration of the honing agent exceeds several%, this tendency becomes remarkable. Therefore, in practice, the concentration to the extent of a few percent is the limit. In the technique described in the above-mentioned patent document, the case where the high-concentration water to be treated is passed through the water is condensed into the pores of the separation membrane of 201235090, or the recovery rate of the honing agent particles is lowered. It is difficult. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2001 - 1 1 3 27 [Patent Document 4] JP-A-2002-83789 [Invention] [Problems to be Solved by the Invention] Generally, in the filtration treatment via the separation membrane, when the concentration of water to be treated exceeds a certain concentration At this time, the speed at which the screen of the membrane is clogged is rapidly increased. As described earlier, in the case of honing the slurry, when the concentration of the honing agent exceeds several %, the clogging of the sieve holes is imminent. Therefore, in the prior art such as wastewater treatment, the concentration of the solid component is actually a limit of several %, and among these concentrations, the CMP project is directly reused as a honing slurry. For the sake of difficulty. Further, in the case of using a hollow type separation membrane, when the concentration of the honing agent in the slurry is concentrated to more than several %, as described above, in the hollow interior, the subsequent deposition of gelation proceeds. When the concentration treatment is further continued, as shown in Fig. 8, it is clearly understood that the gel-like honing agent is deposited on the side of the treated water outlet of the hollow system. When it is in this state, it is impossible to get -8 - 201235090 to the concentrated water, and it is impossible to continue using the module itself. Moreover, since the honing agent is deposited in a gel form, the recovery rate of the honing agent is drastically lowered. The present invention has been made to solve the above problems, and an object thereof is to provide a honing agent capable of suppressing an increase in pressure loss or a large reduction in recovery rate through clogging of a film, and concentrating the honing agent into a high concentration. The recovery device and the recovery method of the honing agent. [Means for Solving the Problem] In order to achieve the above object, the inventors of the present invention conducted a keen review, as described above, on the gelation of the separation surface of the separation membrane, or the gel of the honing agent on the side of the water to be treated. Whether or not the accumulation of the substance is found to depend mainly on the effective filtration length of the separation membrane is completed until the invention of the present application is completed. The honing agent recovery device of the present invention is a device for recovering a honing agent from a used honing slurry used in a CMP project, characterized in that the honing agent recovery device has a 导入 imported into the use 前述The pores of the grinding slurry are cylindrical separation membranes, and the length of the effective filtration portion of the pores of the separation membrane is 0. 8 m or less, the honing agent recovery apparatus concentrates the concentration of the honing agent of the used honing slurry to a concentration of 1% by mass or more. The concentration of the honing agent to be introduced into the separation membrane is not particularly limited because it depends on the concentration of the liquid discharged from the customer's factory, but in general, it can be introduced as 0. 02 to 5 mass% of the composition of the used slurry. In the hollow portion of the separation membrane, it is preferred that the used honing slurry is passed through by a cross-flow method. It is preferable that the separation membrane is provided in an internal pressure type membrane separation unit. The separation membrane is preferably a hollow membrane. The inner diameter of the separation membrane is 0. 1 mm -9- 201235090 or more 0. Preferably, the separation molecular weight of the separation membrane is 3,000 to 3 Å, and 〇 is preferable. The above separation membrane is preferably composed of any of polyethylene, tetrafluoroethylene, polyvinylidene fluoride, polypropylene, cellulose acetate, polypropylene, polyimine, poly maple or polyether. The honing agent recovery device is in the front stage of the separation membrane, and has an effective filtration length longer than the separation membrane, and can be used as a separation membrane having a cylindrical passage. The length L1 of the effective filter portion of the foregoing separation membrane is 0. 8~1. 5m, the length L2 of the effective filter portion of the separation film disposed at the rear stage of the preceding stage separation membrane is 0. 2~0. 8 m or less is preferred. The method for recovering the honing agent of the present invention is characterized in that the honing slurry used in the CMP project is used, and the water passing through the tunnel is cylindrical, and the length of the effective filtering portion is 0. The separation membrane of 8 m or less can concentrate the concentration of the honing agent of the used honing slurry to a concentration of 1 〇 mass% or more. In the hollow portion of the separation membrane, it is preferred that the used honing slurry is passed through a cross-flow method. In addition, the inner diameter of the separation membrane is 0. 1mm or more 0. 8mm or less is preferred. Further, the circulating flow rate of the treated water in the effective filtration portion of the separation membrane is 0. 5~2m/SeC is preferred. It can be used as a first filtration system in which a turpent slurry used in a CMP project is passed through water to concentrate the honing slurry used in the CMP project, and the first pulverizing slurry is used. The length of the effective filter is 0. a second filtration process in which the membrane is separated in a subsequent stage of 8 m or less, and the concentrated water of the first separation membrane is passed through water and concentrated. As the separation membrane of the preceding stage, an effective filtration length longer than that of the latter separation membrane is used. Separation membrane. In the first filtration project described above, the concentration of the honing agent depending on the drainage of the customer's workshop -10- 201235090 is not particularly limited. Generally, the filtration is 0. 02 to 5 mass% of the used honing slurry is concentrated to a maximum of 13% by mass, more preferably to 9 to 1% by mass. In the second filtration process, the filtration is performed in the first filtration. Concentrated water of 13% by mass or less obtained by the project is concentrated to a maximum of 26% by mass, more preferably 20 to 25% by mass. Further, the method for recovering the honing agent is preferably a polishing apparatus for honing agent of the present invention. [Effects of the Invention] As the recovery device for the used honing agent according to the present invention, the separation of the gelled surface of the filter surface, or the water to be treated, by the use of the separation membrane having a length of the effective filtration portion of a specific enthalpy or less Defects such as gelation of the honing agent on the outlet side are less likely to occur. Therefore, the slurry can be concentrated to a concentration of the honing agent of the order of more than ten percent. In addition, the honing slurry used after the CMP project can be concentrated to a high concentration with a lower energy than the conventional one, and can be used as a product to recover the concentrated honing agent to a high concentration. Slurry. Further, by performing concentration at a high concentration, it is possible to suppress an increase in pressure loss in the film or to block the separation membrane, and it can be used as a recovery device for a honing agent which suppresses a marked decrease in the recovery rate. In the recovery method of the honing slurry, the recovery rate is not significantly lowered, and as a product, it is possible to use a possible level to recover the concentrated honing agent as a high-concentration slurry. As a result, the amount of the new slurry used in the CMP project can be reduced by 60% or more. -11 - 201235090 [Embodiment] Hereinafter, the recovery device of the honing agent and the recovery method of the honing agent of the present invention will be described in detail. (First Embodiment) Fig. 1 is a schematic block diagram showing a recovery device for a honing agent according to an embodiment of the present invention. In the honing agent recovery apparatus 1 of the present embodiment, coarse particles of the used honing slurry S (hereinafter referred to as used honing slurry S) after being removed from the honing semiconductor are removed by CMP engineering. The protective filter 2, and the processing container tank 3 for accommodating the treated water of the protective filter 2, and the membrane separating portion 4 having the separation membrane 41 for filtering the used honing slurry S are sequentially arranged along the flow path. Settings. However, the protective filter 2 is a structure in which a honing agent or a solid impurity having a large particle diameter generated by clotting of a burr pad or the like when honing a semiconductor crystal is entangled. The protective filter 2 is configured to have a larger pore diameter than the honing agent particles, and is not particularly limited and can be used. The protective filter 2 and the processing container tank 3 are connected via a pipe 5. The processing container tank 3 and the membrane separation unit 4 are connected via a pipe 6 having a pump P1. However, a component concentration meter C1 is provided for the processing container tank 3. The membrane separation unit 4 is connected to a permeated water outlet pipe 7 and a concentrated water outlet pipe 8 having a switching valve B1. The concentrated water outlet pipe 8 is supplied with an opening supplied to the concentrated water recovery container tank 9 by the concentrated water supplied to the membrane separation unit 4. The upper portion of the on-off valve B1 of the concentrated water outlet pipe 8 and the treatment chamber -12-201235090 are provided with a lock via the on-off valve B1 and an opening of the on-off valve B2, which is obtained in the membrane separation unit 4. The concentrated water is returned to the reflux pipe 1 of the processing vessel tank 3. The separation membrane 41 has a cylindrical channel. The inside of the tunnel or the outside thereof is concentrated by removing excess water from the used honing slurry S by the used honing slurry S. As the first separation membrane 41 having a cylindrical pore, for example, a hollow membrane type, a tubular type, or a flat membrane type separation membrane can be suitably used. Among these, the separation membrane of the hollow type is space-saving and has a large membrane area, and is preferably used as the separation membrane 41. The length L of the effective filter portion of the separation membrane 41 is concentrated to a concentration of 0. Below 8m, the ideal is 〇. 5m or less, more ideally. 3m or less. In general, for example, in the case of a hollow type separation membrane, when a high concentration slurry is passed through a separation membrane, the concentrated water passes through the effective filtration portion thereof on the filtration surface 41 2 of the hollow system 410. Solid content is deposited. Further, when the water is continuously supplied, the gel layer is formed by the solid component deposited on the filter surface 412, and the thickness thereof is increased (see Fig. 2). The gel layer on the filtering surface 4 1 2 of the separation membrane 41 is formed to be more easily formed as the effective filtration length is longer. By the formation of the gel layer, the effective inner diameter 4 1 0 S of the hollow system 410 is narrowed and there is an increase in pressure loss, or occlusion of the film, and the recovery efficiency of the honing agent is remarkably lowered. In addition, the gel layer or the gel-like deposit is formed by the honing agent particles, accompanied by. As the gel layer increases or gelatinous deposits are formed, the recovery of the honing agent particles decreases. Further, as shown in Fig. 8, the abrasive agent was deposited in a gel form on the side of the treated water outlet of the hollow system, and the continuation of the filtration treatment became difficult. In addition, the amount of medicine or washing time required for washing the filter surface increases. It is the reason for the increase in the cost required for the entire honing agent recovery project. In the honing agent recovery device 1 of the present invention, as the separation membrane 41, the length L of the effective filter portion is 0. Below 8m, ideally 0. Below 5m, more ideally. A separation membrane of 3 m or less. In the case of using an effective filter length module of such a specific size or less, even if a high-concentration used slurry is passed through water, it is less likely to cause screen plugging. Therefore, while the growth of the gel layer on the filtering surface 412 is suppressed, gel-like deposition does not occur. In the meantime, even if the water having a high concentration of the water to be treated is passed through, the recovery device 1 can be suppressed as the pressure loss of the separation membrane 41 is increased, or the membrane is less likely to be blocked, and the recovery rate is remarkably lowered. Further, as described above, when the gel layer is formed on the filtration surface 412, coarse particles in which the honing agent particles are gelled are peeled off from the gel layer and mixed in the water to be treated. When such coarse particles are mixed in the recovered honing agent, scratches are caused on the surface of the wafer when the CMP project is reused, which causes a decrease in the yield of the product. In the honing agent recovery apparatus 1 of the present invention, as the separation membrane 41, a separation membrane whose length L of the effective filtration portion is in the above range is used. Therefore, the formation of the gel layer inside the separation membrane or the formation of coarse particles deposited by the gel-like substance is suppressed, and the amount of coarse particles mixed with the honing agent particles after the recovery is extremely reduced. As a result, even if the CMP project is reused, scratches and the like on the surface of the wafer are hardly generated, and the honing agent which can be honed can be recovered with high precision. -14- 201235090 The length L of the effective filter portion of the separation membrane 41 exceeds 0. In the case of 8 m, the thickness of the gel layer is likely to increase on the filtration surface 412 of the separation membrane 41, and it is easy to cause an increase in pressure loss through the narrowing of the effective inner diameter or clogging of the membrane. The length L of the effective filter portion of the separation membrane 41 is within the above range, and is 0. More than 2m is preferred. The length L of the effective filter portion of the separation membrane 41 is less than 0. At 2 m, the number of modules of the separation membrane 41 provided in the recovery device 1 increases, and it becomes difficult to provide an appropriate filtration treatment device. The length L of the effective filter portion of the separation membrane 41 is preferably 0. 2~0. 3m. The separation membrane 41 may be an organic membrane made of an organic material, and an inorganic membrane made of an inorganic ceramic may be used. As the organic film, for example, polyethylene (PE), tetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polypropylene (PP), cellulose acetate (CA), and polypropylene (optional) can be preferably used. PAN), polyimine (PI), polyfluorene (PS), polyether fluorene (PES), etc. Further, as the inorganic film, alumina (Al 2 〇 3 ), chromium oxide (Zr 〇 2 ), Ceramic material of titanium oxide (Ti02), or stainless steel (SUS), glass (SPG), and the like. Among these, as the separation membrane 41, polyfluorene (PS) or polyether oxime (PES) can be preferably used. The separation membrane 41 may have a hollow-type shape, and may be a fine filtration membrane or an additional filtration membrane. From the viewpoint of the most efficient recovery and recovery of the honing agent particles in the concentrated liquid, the separation membrane 41 is preferably adapted to use an additional filtration membrane. The separation membrane 41 preferably has a molecular weight of 3,000 to 30,000. When the molecular weight of the separation film -15-201235090 is less than 3,000, the supply pressure of the separation membrane 41 must be increased in order to obtain water permeated into the separation membrane 41 by the water to be treated. Therefore, at the same time as the energy efficiency is lowered, there is a fear of damage to the separation membrane 41. On the other hand, when the molecular weight of the separation membrane 41 exceeds 30,000, a part of the honing agent particles moves to the permeate side through the separation membrane 41, and the ruthenium particles cannot be efficiently recovered. Further, in this case, the fine particles having a diameter which is slightly the same as the pore diameter of the separation membrane 41 are apt to block the pores of the separation membrane 41, and the sieve pores are clogged. The separation molecular weight of the separation membrane 41 is 6000 to 10000. Better. The separation membrane 41 is a hollow type separation membrane or a tubular separation membrane, and the inner diameter of each hollow system or the like is 0. 1 mm or more 0. 8mm or less is preferred. The inner diameter of each hollow system or the like of the separation membrane 41 is less than 0. At 1 mm, the pressure loss of the water to be treated flowing in the hollow portion of the membrane is increased, and it becomes difficult to obtain appropriate treatment efficiency. Further, in this case, the film surface strength is lowered, and the film is broken due to an increase in the concentration of the water to be treated. On the other hand, the inner diameter of each hollow system or the like of the separation membrane 41 exceeds 0. At 8 mm, the shearing speed of the water to be treated flowing in the hollow portion of the film is small, and other impurities of the honing agent are liable to accumulate on the inner wall of the hollow body, and there is a possibility that the hollow portion is closed. In addition, the gel of the honing agent is generated in a large amount, and the concentration of the honing agent in the concentrate is lowered. In order to increase the shearing speed, it is necessary to increase the equipment, and it will consume a lot of energy, which is not ideal. Furthermore, there is a tendency to reduce the pressure resistance for external pressure. The inner diameter of each hollow system of the separation membrane 41 is 〇. Above 3mm. 8mm or less is more preferable. -16 - 201235090 The membrane separation unit 4 may be an internal pressure type separation portion that passes water to be treated in the hollow system 4i, and the water to be treated is passed through the support layer 411 of the hollow system 410. The separation part of the external pressure type may also be used. In the case where the membrane separation unit 4 is a separation unit that is an internal pressure type, the solid component deposited on the filtration surface 412 is peeled off by the shearing force of the water to be treated in the hollow system 410, thereby suppressing gelation. The growth of the layer is ideal. As the recovery apparatus 1 as described above, the permeated water system obtained from the permeated water outlet pipe 7 can be recovered and reused. Specifically, for example, it can be used as raw water of an ultrapure water device or the like after being treated as untreated or as a treatment corresponding to the water quality of the permeated water. In addition, it can be used as other functions in the workshop, such as domestic water, cooling tower water, etc. (Second Embodiment) Fig. 3 is a schematic block diagram showing a honing agent recovery apparatus according to an embodiment of the present invention. In the honing agent recovery apparatus 11 of the present embodiment, the honing slurry S (hereinafter, shown as the used honing slurry S) used after the honing semiconductor is removed by CMP engineering is coarsened. In the subsequent stage of the protective filter 12 for the particles, the front-stage processing container tank 13 for accommodating the treated water of the protective filter 12 is provided with a separation membrane (hereinafter referred to as a first separation membrane) 141 for filtering the used honing prize s. The previous stage membrane separation unit (hereinafter referred to as the first membrane separation unit) 14 is sequentially disposed along the flow path. However, the protective filter 12 captures the solid impure -17-201235090 which is formed by the honing agent or the honing of the semiconductor wafer, such as honing padding and the like. The protective filter 12 is not particularly limited as long as it has a larger particle diameter than the honing agent particles. The protective filter 12 and the front processing container tank 13 are connected via a pipe 15. The front stage processing container tank 13 and the first membrane separation unit 14 are connected via a pipe 16 having a pump P2. However, a component concentration meter C2 is provided for the front-stage processing container tank 13. In the first stage of the membrane separation unit 14 of the first step, the concentrated water separated by the first membrane separation unit 14 is accommodated (hereinafter, the first concentrated water is shown). 1 7 ' and a subsequent separation membrane (hereinafter, shown as a second separation membrane) 181 having a first concentrated water supplied from the downstream processing vessel tank 17 (hereinafter, shown as a second section) The membrane separation unit 18 and the recovery container tank 19 for recovering the concentrated water separated by the second membrane separation unit 18 (hereinafter, the second concentrated water is shown). However, a component concentration meter C3 is provided for the rear stage processing container tank 17. The first membrane separation unit U and the downstream processing vessel tank 17 are connected via a pipe 20 having an on-off valve B3. The rear stage processing tank tank 17 and the second membrane separating unit 18 are connected via a pipe 2 1 having a pump P3. The first permeated water outlet pipe 22 is connected to the first membrane separation unit 14 . Further, between the front stage of the opening and closing valve B3 of the pipe 20 and the front stage processing container tank 13, the opening of the switching valve B3 and the opening of the opening and closing valve B4 are provided, and the first film separating unit 14 is obtained. The concentrated water is returned to the reflux pipe 23 of the front-stage processing vessel tank 13. The second membrane separation unit 18 is connected to a second permeated water outlet pipe -18-201235090 24 and a concentrated water outlet pipe 25 having an on-off valve B5. The concentrated water outlet pipe 25 is opened by supplying the concentrated water supplied to the second membrane separation unit 18 to the recovery container tank 19. The upper portion of the on-off valve B5 and the rear-stage processing container tank 17 of the concentrated outlet water pipe 25 are provided with a lock via the on-off valve B5 and an opening of the on-off valve B6, which is obtained in the second membrane separation unit 18. The concentrated water of 2 is refluxed to the reflux piping 26 of the subsequent processing vessel tank 17. In the first separation membrane 141, the second separation membrane 181 has a cylindrical pore. The inside of the tunnel or the outside thereof is concentrated by removing excess water from the used honing slurry S by the used honing slurry S. As the first separation membrane 141 having a cylindrical pore, for example, a hollow membrane type, a tubular type, or a flat membrane type separation membrane can be suitably used. Among these, the separation membrane of the hollow type is space-saving and a large membrane area can be obtained. Therefore, the first separation membrane 141 and the second separation membrane 181 are preferably used. The second separation membrane 181 is configured to filter the concentrated water provided in the first separation membrane 141 of the preceding stage and further concentrate it to increase the concentration of the honing agent. The length L2 of the effective filter portion of the second separation membrane 181 is 0. Below 8m, ideally 0. 5m or less, more preferably 0. 3m or less. In the second separation membrane 181, even if the separation membrane having the above-described effective filtration length is used, even if the slurry having a high concentration is used to pass the water, the membrane pore clogging is unlikely to occur, and the growth of the gel layer is suppressed. Therefore, it is possible to reduce the pressure loss in the second separation membrane 181 or to prevent the membrane from being occluded, and the recovery rate of the recovery rate is remarkably lowered. -19- 201235090 The length L2 of the effective filter portion of the second separation membrane 181 exceeds 0. In the case of 8 m, on the filter surface of the second separation membrane 181, the thickness of the gel layer is apt to increase, and the pressure loss due to the narrowing of the effective inner diameter is likely to occur, or the membrane is occluded. The length L2 of the effective filter portion of the second separation membrane 181 is particularly preferably the same as that of the separation membrane 41 of the first embodiment. 2 ~ 〇. 3 m. The length L2 of the effective filter portion of the second separation membrane 181 is preferably formed shorter than the length L1 of the effective filter portion of the membrane 141. In other words, it is preferable that the length L1 of the effective filter portion of the first separation membrane 141 is longer than the length L2 of the effective filter portion of the second separation membrane 181. Thereby, in the first separation membrane 141, the used honing slurry S diluted at a low concentration by the dispersion medium is efficiently filtered, and in the second separation membrane 181, The first concentrated water obtained in the separation membrane 141 of 1 is further subjected to filtration treatment. Thus, the honing agent particles are concentrated to a high concentration slurry as a possible level of reusability of the product, and recovered at a low energy. In recent years, the used honing slurry discharged from the CMP project has a considerable discharge of more than 10 μm. Therefore, a technique for recovering the honing agent component while removing and recovering the water contained in the slurry by a more efficient treatment is required. In the present embodiment, the first separation membrane 141 having a large membrane area is provided as the second-stage constituent as described above, and the volume of the water to be treated can be greatly reduced while being provided in the latter stage. The separation membrane I 8 of 2 did not cause clogging of the sieve, and the treated water was concentrated to a higher concentration of -20-201235090 degrees. Therefore, in comparison with the first embodiment, the number of modules used can be reduced. The length L2 of the effective filter portion of the second separation membrane 181 is equal to or exceeds the length L1 of the first separation membrane 141, and the thickness of the gel layer is likely to increase inside the second separation membrane 181. However, it is easy to cause an increase in pressure loss through the narrowing of the effective inner diameter or occlusion of the membrane. The length L1 of the effective overturn portion of the first separation membrane 141 is not particularly limited, but the membrane area is considered to be the same. 8~1. 5m is better. The length L1 of the effective filter portion of the first separation membrane 141 is less than 0. At 8 m, the number of modules having the separation membrane 141 provided in the recovery device 11 is increased, and the installation area is increased, so that a sufficient effect cannot be obtained as a recovery device. On the other hand, the length L1 of the effective filter portion of the first separation membrane 141 exceeds 1. At 5 m, there is a limit to the height of the first separation membrane 141, and the separation and removal of the separation membrane 141 becomes difficult. The length L1 of the effective filter portion of the first separation membrane 141 is more preferably 0. 8~1. 5m. The first separation membrane 141 is configured to have a cylindrical pore shape, and may be a fine filtration membrane, and an additional filtration membrane may be used. It can be optimally applied and efficiently. The honing agent particles (abrasive grains) are recovered, and the particle size of the honing agent particles in the recovered concentrated liquid is kept constant, the pore diameter is small, and an additional filter film with good energy efficiency is further provided. Further, the second separation membrane 181 may have a hollow-type shape, and may be a fine filtration membrane or an additional filtration membrane. The additional filtration membrane can be optimally applied from the viewpoint of maintaining the recovery rate of the honing agent particles in the highly recovered concentrated liquid. -21 - 201235090 The separation molecular weight of the first separation membrane 141 and the second separation membrane 181 is preferably 3,000 to 30,000. When the fractional molecular weight of the first separation membrane 141 and the second separation membrane 1 81 is less than 3,000, in order to obtain water permeated into the separation membrane by the water to be treated, it is necessary to increase the supply pressure to the separation membrane. Therefore, while the energy efficiency is lowered, there is a fear of damage to the separation membrane. On the other hand, when the divisional molecular weight of the first separation membrane 141 and the second separation membrane 181 exceeds 30,000, a part of the honing agent particles is moved to the permeate side by the first separation membrane 141, and there is a flaw. The recovery efficiency of the abrasive particles is reduced. Further, in this case, the fine particles having a diameter which is slightly the same as the diameter of the separation membrane 141 facilitate the clogging of the pores of the separation membrane 141 and the second separation membrane 118, which may cause clogging of the sieve. The first separation membrane 141 and the second separation membrane 181 are in the form of a hollow separation membrane or a tubular separation membrane, and have an inner diameter of 0. 1mm or more 0. 8mm or less is preferred. The inner diameter of each hollow system or the like of the first separation membrane 141 is less than 0. At 1 mm, the pressure loss of the treated water flowing in the hollow portion of the membrane increases, and it becomes difficult to obtain appropriate treatment efficiency, and the membrane surface strength of the separation membrane 141 decreases, accompanied by the concentration of the treated water. The film rises and the film breaks. On the other hand, the inner diameter of each hollow system or the like of the first separation membrane 141 is 0. When the thickness is 8 mm or more, the shearing speed of the treated water flowing in the hollow portion of the membrane is small, and the honing agent or other impurities are likely to accumulate on the inner wall of the hollow portion, and the hollow portion is occluded, and the honing agent particles are condensed. The gel is produced in large amounts, and the concentration of the honing agent in the concentrated liquid after the recovery is lowered. The first separation membrane 141 and the second separation membrane 181 are hollow-system internal diameter systems. 3mm to -22- 201235090 on 0. 8mm or less is more preferable. The first separation membrane 141 and the second separation membrane 181 may be organic membranes made of an organic material, and inorganic membranes made of inorganic ceramics may be used. As the organic film, for example, polyethylene (PE), 4-fluorinated ethylene (PTFE), polyvinylidene fluoride (PVDF), polypropylene (PP), cellulose acetate (CA), and polypropylene can be preferably used. (PAN), polyimine (PI), polyfluorene (PS) and polyether maple (PES). Further, as the inorganic film, a ceramic material of alumina (ai2o3), chromium oxide (Zr〇2), titanium oxide (Ti02), or stainless steel (SUS), glass (SPG) or the like can be used. Among these, as the first separation membrane 141 and the second separation membrane 181, polyfluorene (PS) or polyether maple (PES) can be preferably used. In the case where the first separation membrane 141 and the second separation membrane 181 are hollow separation membranes, they may be treated as internal pressure type separation portions that pass water to be treated inside the hollow system. The water-passing water may be separated from the outer side of the support layer of the hollow system. In the case of the internal pressure type separation unit, the solid component deposited on the filtration surface is peeled off by the shearing force of the water to be treated in the hollow system, and the growth of the gel layer can be suppressed. . In the recovery apparatus 11 as described above, the thin solution of the slurry can be concentrated to a certain extent via the first separation membrane 141, and a large amount of CMP drainage can be efficiently concentrated. In particular, in a semiconductor factory having a large manufacturing scale, it is equivalent to a displacement of 1,000 tons or more. However, by providing the first separation membrane 141, such a large amount of drainage can be reduced to about 1/10 to 1/500. The amount of -23- 201235090. As a result, in comparison with the first embodiment in which the first separation membrane 141 is not provided, the number of module assemblies provided as a whole can be reduced, and the honing agent recovery device 11' of the present invention is lifted. The description has been made by way of example, but the configuration may be changed as appropriate without departing from the scope of the invention. Next, a method of recovering the honing agent using the honing agent recovery apparatus 11 of the present invention will be described with reference to Fig. 3 . In the present embodiment, the second separation membrane 181 is the first separation membrane 181, and the recovery device 11 using the honing agent having the hollow filtration type additional filtration membrane will be described. The first separation membrane 141 is formed of a cylindrical channel, and may not be a hollow membrane. It can also be a tubular or flat film type. The honing slurry S used in the treatment object is not particularly limited as long as it is a honing agent contained in the CMP project (chemical mechanical honing engineering). Examples of such a honing agent particle include halogen particles, ruthenium particles, and the like. As a honing agent particle system, the best use of the average particle diameter is 〇. 〇1~Ιμηι composition. The average particle diameter of the honing agent is suitably selected by CMP engineering, but is, for example, 0. 04~0. 4μιη. First, the used honing slurry S used in the CMP project is supplied to the protective filter 12 via the pipe 15. The used honing slurry S is stored in the front stage processing tank tank 13 after removing coarse particles having a particle diameter of several tens of μη or more by the process of the protective filter 12. The concentration of the honing agent particles in the untreated stage of the used honing slurry S is not particularly limited depending on the customer's workshop. The honing agent concentration of the honing slurry s used in the CMP work -24 - 201235090 is usually 〇· 02~5 mass%. The used honing slurry S stored in the front-stage processing container tank 13 is in a state in which the opening and closing valve B3 is closed, and the opening and closing valve B4 is opened, and is supplied to the separation membrane 141 having the first pressure via the pipe P2 through the pipe 16. The first membrane separation unit 14. The used honing slurry S is passed through the protective filter 12 to remove coarse particles having a particle diameter of several tens of μm or more, and then water is supplied to the inside of each hollow system of the first separation membrane 141 by a cross flow method. In the process of passing through the effective filter unit, the excess water is passed through and concentrated (the first filtration process). At this time, the dispersion medium of the used honing material S and the like are passed through the separation membrane 141 and the honing agent particles flowing out of the honing slurry S used in the permeated water outlet pipe 22' remain in the first separation. The first concentrated water side of the concentrated water of the membrane 14 1 . The first concentrated water is returned to the front stage processing tank 13 through the return pipe 23. After the continuation of the work at a specific time, the concentration of the honing agent in the treated water in the container tank 13 in the previous stage measured by the component concentration meter C2 becomes a maximum of 13% by mass, and more preferably in the stage of 9 to 10% by mass. The switching valve Β 3 closes the switching valve Β 4, and a part thereof is supplied to the rear processing container tank 17 through the piping 20. The flow rate of the treated water (the used honing slurry S and the first concentrated water) by the effective filtration portion of the first separation membrane 141 is preferably 〇 5 to 2 m/sec. When the flow rate of the treated water (the used honing slurry S and the first concentrated water) of the first filtration membrane 141 of the first separation membrane 141 is less than m·5 m/see, the filtration surface of the separation membrane 141 is easily formed. There are honing agent particles attached and there is a decrease in the amount of permeate water -25-201235090. In this case, it is necessary to increase the number of the separation membranes 141, and the manufacturing cost of the recovery device 11 becomes high. On the other hand, the flow rate of the treated water in the effective filter portion of the first separation membrane 141 exceeds 2. At 0 m/sec, the amount of liquid that comes into contact with the membrane surface becomes excessive and there is a fever. In this case, the separation membrane 141' concentrate is simultaneously damaged by heat, and there is a possibility of deterioration. In addition, it is necessary to increase the flow rate of the water to be treated of the separation membrane 141, and it is necessary to increase the size of each pipe or valve, and the manufacturing cost of the recovery device 11 becomes high. The effective filter portion of the first separation membrane 141 is passed. The flow rate of the treated water is more preferably 0. 55~1. 5m/sec. The first concentrated water stored in the downstream processing container tank 17 is in the state in which the opening and closing valve B5 is closed, and the opening and closing valve B6 is opened, and the pump P3 is supplied through the piping 21 to be pressurized to the second separator 181 having the second separation membrane 181. The membrane separation unit 18 is provided. The second separation membrane 181 is separated from the first one. The effective filtration length L1 of the membrane 141 is short and has a enthalpy. Below 8m, ideally 0. 5m or less, more preferably 0. Effective filter length L2 below 3m. The second separation membrane 181 is attached to the hollow portion of each hollow system, and the first concentrated water is passed through the water by a cross flow method. The first concentrated water is passed through a process of passing through the effective filtration unit of the hollow system, and is condensed by excess water (second filtration project). At this time, the first dispersion medium of the concentrated water flows out through the separation membrane 181 to the permeated water outlet pipe 24, and the honing agent particles contained in the first concentrated water remain in the concentrated water of the second separation membrane 181. The second concentrated water side. . The flow rate of the water to be treated (the first concentrated water) is 0 by the effective filter portion of the second separation membrane 181. 5 to 2 m/sec is preferred. In the effective filter portion of the second separation membrane 1 81, the flow rate of the treated water is less than 0. At 5 m/sec, it is easy to adhere to the filter surface of the separation membrane 181 on the -26-201235090, and the membrane occlusion is likely to occur. On the other hand, when the flow rate of the water to be treated in the effective filter portion of the second separation membrane 181 exceeds 2 m/sec, an excessive amount of energy is added to the honing agent particles, and the particles are condensed to form a coarse particle. particle. When the coarse particles are mixed in the recovered honing agent, when the CMP project is reused, scratches are formed on the surface of the wafer or the like, and the yield of the product is lowered. Further, when such coarse particles are generated, a gel layer is formed on the filtration surface of the separation membrane, and the cleaning time or the amount of the medicine used is increased. The flow rate of the water to be treated which passes through the effective filter portion of the second separation membrane 181 is more preferably 〇. 6~lm/sec. After the processing of the above-mentioned processing is continued at a specific time, the switching valve B5 is turned on, and the switching valve B6 is closed, at the stage where the concentration of the honing agent of the stored water in the processing tank 17 is measured to be the target concentration by the component concentration meter C3. A part thereof is supplied to the recovery container tank 19 through the piping 25. The concentration of the stored water in the subsequent processing vessel tank 17 when it is supplied to the recovery vessel tank 19 through the piping 25 is preferably 10% by mass or more, and the maximum is 26% by mass, more preferably 20 to 25% by mass. On the filtering surface of the second separation membrane 181, the pressure loss of the treated water is O. IMPa is better than 0. Below 08 MPa is more preferred. In the method for recovering the honing agent of the present invention, the second separation membrane 181 having the effective filtration length shorter than the first effective filtration length is used, and the pressure loss on the filtration surface of the second separation membrane is suppressed. The increase, or the occlusion of the film, at the same time as the product can be used as a level, can efficiently recover the honing agent particles concentrated to a high concentration of the used honing slurry S. -27-201235090 However, in the present embodiment, the first filtration process is shown, and the second filtration process simultaneously passes the water to be treated to the hollow portion of the hollow system, and the filtration process is performed by the internal pressure type. However, the present invention is not necessarily limited to such a form. For example, the water to be treated may be filtered to the outside of the hollow system, and the filtration may be carried out in an external pressure type. The permeated water obtained by the first permeated water outlet pipe 22 and the second permeated water outlet pipe 24 can be recovered and reused. For example, it can be used as raw water of an ultrapure water device or the like after being treated as untreated or as a treatment corresponding to the water quality of the permeated water. In addition, it can also be used as other functions in the workshop, such as domestic water, cooling tower water, etc. [Examples] Hereinafter, the present invention will be described in detail by way of examples and comparative examples. (Example 1) A filtration treatment of a slurry used in a CMP process was carried out using the honing agent recovery apparatus 1 shown in Fig. 1 . In the pump P1 of Fig. 1, a levitro pump "LEV300" (manufactured by IWAKI Co., Ltd., trade name) is used as the membrane separation unit 4, and a hollow type UF membrane module "FB02-VC-FUST6 5 3" is used. (made by Daicen Membrane Systems Co., Ltd., trade name). As the processing container tank 3, the concentrated water recovery container tank 9 is a concentrated container tank (made of PVC). The hollow type UF membrane module "FB02-VC-FUST653" is divided into molecular weight; 6000, hollow inner diameter; 0_5mm, membrane area: -28- 201235090 0. 5m2, effective filter length; 0. 26m. First, the concentration of the honing agent is about 1% by mass (pH: 9. 8) The used honing slurry solution 'is supplied from the pipe 5 through the protective filter 2 to the processing container tank 3. Then, the on-off valve B1 is closed, the on-off valve B2 is opened, and the used honing slurry in the processing container tank 3 is passed through to the membrane separation unit 4. The circulating flow rate in each pipe of the used slurry was taken as 8. 1 L/min, the line speed in the hollow mesothel 41 is 0. 5 5m/sec. Further, in the hollow film 41, the pressure near the inlet of the used honing slurry becomes 0. 2MP a ground, the number of impeller rotations of the pilot PI (levitro pump), and the degree of switching of the on-off valve B2 in the subsequent stage of the membrane separation unit 4. In this state, the water-passing treatment was carried out, and the concentration of the honing agent in the processing container tank 3 measured by the component concentration meter C1 and the amount of permeated water discharged from the permeated water outlet piping were measured. (Example 2) As the membrane separation unit 4, the used honing slurry was used in the same manner as in Example 1 except that the hollow type UF membrane module "M8 1S6000 1N" (manufactured by SPECTRUM Co., Ltd.) was used. The water-passing treatment was carried out in the same manner as in Example 1 to measure the concentration of the honing agent in the processing vessel tank 3. However, the hollow type UF membrane module "M81S6000 1N" is the inner diameter of the hollow system; 5mm, effective filter length; 〇. 46m. (Example 3) As the membrane separation unit 4, the use of the hollow-type UF membrane module "KM1S60001N" (manufactured by SPECTRUM Co., Ltd.) was carried out in the same manner as in Example 1 of -29-201235090. The water-passing treatment of the material was carried out in the same manner as in Example 1 as the concentration of the honing agent in the measurement container tank 3. However, the hollow type UF membrane module "KM1S6000 1 N" is a hollow system inner diameter: 〇. 5mm, effective filter length; 〇. 63m. (Comparative Example 1) As the membrane separation unit 4, a water-based UF membrane module "KM1S30001N" (trade name, manufactured by SPECTRUM Co., Ltd.) was used as the water for the used honing slurry as in the first embodiment. The treatment was carried out in the same manner as in Example 1 as the concentration of the honing agent in the measurement container tank 3. However, the hollow type UF membrane module "KM1S3000 1N J series hollow system inner diameter; 0. 5mm, effective filter length; 〇. 81m. (Comparative Example 2) The film separation unit 4 was used in the same manner as in Example 1 except that the hollow-type UF membrane module "AMK-VC-FUST653 j (manufactured by Daicen Membrane Systems Co., Ltd.)" was used. The water-passing treatment of the honing slurry was carried out in the same manner as in Example 1 as the concentration of the honing agent in the measuring container tank 3. However, the hollow-type UF membrane module "amk-vc-fustgss" was the inner diameter of the hollow system; Hey. 5mm, effective filter length; 1. 0m, membrane area; 1. 5m2. In the first embodiment and the comparative example 2, the relationship between the concentration of the honing agent in the processing container tank 3 measured by the component concentration meter c1 and the amount of the permeated water discharged from the permeated water discharge port pipe 7 is shown. In Figure 4. -30-201235090 However, in Fig. 4, the broken line shows the amount of permeated water from the permeated water outlet pipe 7 of the first embodiment, and the solid line shows the amount of permeated water from the permeate outlet pipe 7 of the comparative example 2. Further, in Table 1, it is shown that the hollow inner diameter 'membrane area of each of the hollow separation membranes 4 of Comparative Examples 1 to 2, the effective filtration length, and the material at the same time as in the first to the beginning of the water flow. The concentration of the treated water abrasive and the concentration of the treated water honing agent at the time when the concentration treatment becomes impossible (concentration possible maximum concentration) ° [Table 1] Inner diameter of the hollow system [mm] Membrane area [m2] Effective filtration length [ m] Material treated water honing agent concentration (point at the start of water flow) [% by mass] Water honing agent concentration (point at the end of filtration treatment) [% by mass] Example 1 0. 5 0. 50 0. 26 PES1) 1 25 Example 2 0. 5 6. 6 0. 46 PS2) 1 22 Example 3 0. 5 8. 2 0. 63 PS 1 20 Comparative Example 1 0. 5 11. 2 0. 81 PS 1 17 Comparative Example 2 0. 5 1. 5 1. 0 PES 1 13 1 ) Polyether Maple 2) Poly Maple It is clearly understood from Table 1 that the effective filtration length of the separation membrane 41 is 0. In the recovery apparatus of Examples 1 to 3 of 8 m or less, at the point of completion of the filtration treatment, treated water having a high concentration of a honing agent having a concentration of 2% by mass or more can be obtained, and it is considered that the effective filtration length becomes shorter. The maximum concentration may increase. On the other hand, it has more than 〇. In the recovery apparatus of Comparative Example 1 having an effective filtration length of 8 m, the maximum concentration of concentration may be less than 20% by mass, and -31 - 201235090 is considered to be likely to cause clogging of the mesh in a high concentration range. Further, as shown in FIG. 4, as the membrane separation portion 4, the use has more than 0. In the recovery apparatus of the comparative example 2 of the separation membrane 41 having an effective filtration length of 8 m, when the Si concentration of the water to be treated exceeds 13% by mass, the amount of permeate water is rapidly reduced, and it is difficult to perform the above filtration treatment. . On the other hand, as the membrane separation section 4, it has a crucible. In the recovery apparatus of the first embodiment of the separation membrane 41 having an effective filtration length of 8 m or less, even if the concentration of the water to be treated exceeds 20% by mass, there is no sudden decrease in the amount of permeated water, and even if the treated water is at a high concentration, It can be safely filtered. From the above results, as the membrane separation unit 4, the effective filtration length was 0. In the case of the separation membrane 41 of 8 m or less, it is considered that the used slurry having a low concentration discharged from the CMP project can be stably concentrated to a high concentration range. The liquid discharge system of the honing agent particles containing the cerium oxide particles or the like is required to comply with the drainage standard, and has been subjected to solid-liquid separation from the past. However, even if an additional filtration membrane is used for solid-liquid separation, the concentration limit of the solid component is about several percent. When the concentration of the abrasive component is several percent, it is difficult to reuse the CMP project as a honing slurry, and the solid component is generally disposed of as industrial waste. In the present invention, as shown in Examples 1 to 3, the concentration of the honing agent from the drainage of the CMP project can be concentrated as a product to a concentration of 25% possible, and the recovered product can be recovered. The concentrate is reused in the CMP process to achieve high reuse efficiency. Then, in the recovery device 1 of the honing agent used in the first embodiment, the pressure in the treated water inlet of the membrane separation unit 4 is the same as in the first embodiment, and the pressure loss of the -32-201235090 separation membrane is changed. Examples 4 to 5 and Comparative Examples 3 to 6. (Example 4) The line speed in the hollow film 41 was taken as 0. 6 m/sec, the other conditions were the same as in the first embodiment, and the used honing slurry was passed through water to the recovery device 1 to perform filtration treatment. After the treatment for 80 minutes, the on-off valve B1 is opened, the on-off valve B2 is closed, and the concentrated water in the membrane separation unit 4 is recovered from the concentrated water outlet pipe 8 to the concentrated water recovery container tank 9. (Example 5) The filtration treatment was carried out in the same manner as in Example 2 except that the following points were changed, and the concentrated water of the membrane separation unit 4 was collected. As the membrane separation unit 4, a hollow type UF membrane module "SLP-1053" is used instead of the hollow type UF membrane module "FB02-VC-FUST653" (product name, hollow type inner diameter, manufactured by Asahi Kasei Co., Ltd.) :1. 4mm, molecular weight: 10,000 membrane area: 0. 12 m2, effective filter length: 0. 20 m, film material: poly maple) 使用 The used honing slurry supplied to the processing vessel tank 3 is used as a honing agent concentration of about 0.8 mass% (pH: 1 0. 5), the circulating flow rate of the used slurry in each pipe is taken as 9. OL/min, the pressure near the inlet of the honing slurry of the hollow membrane 41 is taken as 0. 2 MPa, the line speed in the hollow membrane 41 is taken as 0. 69m/sec. (Comparative Example 3) -33-201235090 The concentrated water of the membrane separation unit 4 was collected as the filtration treatment in the same manner as in Example 2 except that the following points were changed. As the membrane separation unit 4, in place of the hollow-type UF membrane module "FB02-VC-FUST653", a hollow-type UF membrane module "AMK-VC-FUS0181" (manufactured by Daicen Membrane Systems Co., Ltd., trade name, hollow) was used. Internal diameter: 〇 8 mm 'Divided molecular weight: 10000 Membrane area: 0. 5 m2, effective filtration length: 1 m, membrane material: PES) 'The linear velocity in the hollow membrane 41 is taken as 0. 55 m/sec ° (Comparative Example 4) The filtration treatment was carried out in the same manner as in Example 2 except that the following points were changed, and the concentrated water of the membrane separation unit 4 was recovered. As the membrane separation unit 4, a hollow type UF membrane module "AMK-VC-FUS03C1" is used instead of the hollow type UF membrane module "FB02-VC-FUST653" (manufactured by Daicen Membrane Systems Co., Ltd., trade name, hollow Internal diameter: 1. 2 mm, molecular weight: 30000 Membrane area: 0. 3 m2, effective filtration length: 1 m, membrane material: PES), the linear velocity in the hollow membrane 41 is taken as 0. 85 m/sec ° (Comparative Example 5) The filtration treatment was carried out in the same manner as in Example 2 except that the following points were changed, and the concentrated water of the membrane separation unit 4 was collected. As the membrane separation unit 4, "AMK-VC-FUS03C1" is used instead of the hollow type UF membrane module "FB02-VC-FUST653" (Daicen Membrane Systems Co., Ltd. -34-201235090, trade name, hollow diameter : ϊ · 2 mm, molecular weight: 30000 Membrane area: 〇. 3 m2, effective filtration length: 1 m, membrane material: PES), and the linear velocity in the hollow membrane 41 was 1·8 m/sec. (Comparative Example 6) The filtration treatment was carried out under the same conditions as in Example 2 except that the following points were changed, and the concentrated water of the membrane separation unit 4 was collected. "AMK-VC-FUST653" is used as the membrane separation unit 4' instead of the hollow-type UF membrane module "FB02-VC-FUST65 3" (manufactured by Daicen Membrane Systems, Inc., product name, hollow diameter, · 〇 . 5mm' molecular weight: 6000 membrane area: 1. 5m2, effective filtration length: 1 m, membrane material: PES). The line speed in the hollow film 4 1 is the same as in the second embodiment. In Examples 4 to 5 and Comparative Examples 3 to 6, the concentration of the honing agent and the recovery rate of the honing agent recovered in the concentrated water recovery container tank 9 are shown in Table 2. Further, the linear velocity in the hollow film 41 of Examples 4 to 5 and Comparative Examples 3 to 6, the inner diameter of the hollow body, and the concentration of the honing agent in the concentrated liquid calculated from the amount of discharged water, 倂Shown in Table 2. -35- 201235090 [Table 2] Effective filtration length 中空 Hollow system inner diameter [mm] Hollow membrane inner thread speed [m/sec] Concentrate honing agent concentration (calculation 値) [% by mass] Concentrate honing agent concentration ( Determination of simple [% by mass] recovery [%] Example 4 0. 26 0. 50 0. 60 26 25 98 Example 5 0. twenty one. 4 0. 69 25 22 88 Comparative Example 3 1. 0 0. 80 0. 55 17 13 76 Comparative Example 4 1. 0 1. 2 0. 85 22 13 61 Comparative Example 5 1. 0 1. twenty one. 8 22 13 60 Comparative Example 6 1. 0 0. 50 0. 60 17 13 79 It is clear from Table 2 that the effective filter length is 0. Below 8 m, the inner diameter of the separation membrane is 0. 1 mm or more 0. In Example 4 of the separation membrane of 8 mm or less, the concentration of the honing agent of the concentrated liquid after the recovery was more than 25% by mass, and it was confirmed that a higher recovery rate was obtained. Further, in the fifth embodiment in which the inner diameter of the hollow system is increased and the pressure loss is lowered while reducing the effective filtration length, in comparison with the fourth embodiment, a specific amount or more of permeated water can be obtained in a relatively high concentration range. However, the concentration treatment cannot be carried out at 25 mass% or more. In addition, the concentration of the honing agent contained in the concentrated liquid after the recovery is lower than the concentration of the honing agent calculated from the amount of permeated water (calculated 値), and it is confirmed that the diameter of the hollow system (fiber diameter) increases, and the honing is performed. The recovery rate of the agent produced a number of declines. In this case, the abrasive component (the honing agent particle) is adhered to the inside of the hollow system to form a gel layer. The effective inner diameter is considered to be narrow. On the other hand, it is more embarrassing. 8m is the effective filter length of the long, and the inner diameter of the hollow system is 〇. l~〇. In the comparative example 3'6 of the range of 8 mm2, the recovery rate of the honing agent was about 76%, and the concentration of the honing agent contained in the concentrated liquid after the recovery was -36-201235090 degrees, which was lower than the honing calculated from the amount of permeated water. Agent concentration (theoretical 値). In addition, the inner diameter of the hollow system is increased to 1. 2. In Comparative Examples 4 and 5 of mm, the recovery of the honing agent became lower. In this case, the abrasive component (the honing agent particle) is adhered to the inside of the hollow system to form a gel layer, and it is considered that the effective inner diameter is narrowed. . (Comparative Example 7) In the recovery apparatus 1 shown in Fig. 1, an additional filtration membrane "MLE-7101H" (manufactured by Kuraray Co., Ltd., product name 'effective furnace length: 1 m' hollow) was provided as the membrane separation unit 4 Internal diameter: 1. 2mm, fractionation molecular weight: 13000, membrane material: poly maple), for filtration treatment. The filtration treatment is carried out in an internal pressure type of cross flow. The separation membrane gradually occludes from the stage where the concentration of the honing agent contained in the concentrate becomes 14% by mass. After that, the output of the pump is increased, the pressure on the water to be treated is increased, and the filtration process is continued. However, in the stage where the Si concentration of the water to be treated is 19% by mass, the concentration treatment becomes impossible. Fig. 6 shows a state in which the inlet of the membrane separation unit 4 at the time when the filtration treatment cannot be performed, and Fig. 7 shows a part of Fig. 6 in an enlarged manner, and Fig. 8 shows a state in which the outlet of the membrane separation unit 4 is at the same time. As shown in Fig. 8, the membrane separation unit at the time when the concentration treatment is difficult is in the latter stage of the water passage direction of the water to be treated (the outlet of the membrane separation unit 4), and the honing agent is gelled by condensation. The coarse particles are formed into one. As a result, the hollow portion of the separation membrane 41 is occluded, and the continuation of the concentration treatment becomes difficult. -37-201235090 (Example 6) The use of the honing agent recovery device shown in Fig. 3 is performed in the CMP project. Filtration of the slurry. In the pump P2 and P3 of Fig. 3, a levitro pump "LEV3 00" (manufactured by IWAKI, trade name) is used as the membrane separation unit 14 to use a hollow type UF membrane module "AMK-VC-FUST65 3". (made by Daicen Membrane Systems Co., Ltd.), the second membrane separation unit 18 is a hollow type UF membrane module "FB02-VC-FUST653" (manufactured by Daicen Membrane Systems Co., Ltd.). Product name). Further, as the processing container tank 13 and the rear stage processing container tank 17, a processing container tank (made of PE) is used, and as the concentrated water recovery container tank 19, a concentrating tank (made of PVC) is used. The hollow type UF membrane module "AMK-VC-FUST653" of the first membrane separation unit 14 is divided into molecular weight: 6000, hollow inner diameter: 〇. 5mm, membrane area: 1. 5 m2, effective filtration length: 1 m, and the second membrane separation unit 18 of the hollow type UF membrane module "FB02-VC-FUST653" is divided into sub-quantities: 6000, hollow inner diameter: 〇. 5mm, membrane area: 〇. 5m2, effective furnace length: 0. 26 m. First, the concentration of the honing agent is about 1% by mass (pH: 9. 8) The used honing slurry solution is supplied from the piping 15 through the protective filter 12 to 200 L to the processing vessel tank 13. Then, the on-off valve B3 is turned off, and the on-off valve B4' is turned on to discharge the used honing slurry in the processing container tank 13 to the first membrane separation portion 14. The circulating flow rate in each pipe of the used slurry was taken as 8. The linear velocity in the 0 L/min' hollow membrane 141 was 〇7 m/sec. In addition, -38- 201235090 'the pressure near the inlet of the 硏 黎 在 stream in the hollow membrane 141' becomes 〇. The degree of rotation of the impeller rotation of the pump P2 (levitro pump) and the switching degree of the on-off valve B4 of the subsequent stage of the membrane separation unit 14 are 2 MPa. In this state, the water-passing treatment was carried out, and the concentration of the honing agent in the processing container tank 3 measured by the component concentration meter C2 was measured. 9 mass%, the amount of permeated water (fiux) discharged from the permeated water outlet pipe 22. At this time, the used honing slurry in the processing tank 13 was about 22 liters. Next, the on-off valve B4 is closed, the on-off valve B3 is opened, and the used honing slurry in the processing container tank 13 is supplied in full to the rear-stage processing container tank 17. Then, the on-off valve B5 is closed, the on-off valve B6 is opened, and the used honing slurry in the rear stage processing container tank 17 is passed to the second membrane separation portion 18. The circulating flow rate in each pipe of the used slurry is 8. OL / min, the line speed in the hollow mesangial 181 as a 〇. 7m/sec. Further, in the hollow film 181, the pressure near the inlet of the used honing slurry becomes 0. At 2 MPa, the number of impeller rotations of the pump P3 (levitro pump) and the degree of switching of the on-off valve B6 in the subsequent stage of the membrane separation unit 18 are modulated. In this state, the water-passing treatment was carried out, and the concentration of the honing agent in the processing container tank 3 measured by the component concentration meter C3 was measured to a volume of permeated water discharged from the water-permeable outlet pipe by 25% by mass. In the sixth embodiment, the relationship between the concentration of the honing agent in the processing container tank 13 measured by the component concentration meter C2 and the amount of the permeated water discharged from the first permeated water discharge pipe 22, and the component concentration The relationship between the concentration of the honing agent in the processing container tank 17 measured by C3 and the amount of permeated water discharged from the second permeated water discharge pipe 24 is shown in Fig. 5. However, the solid line shows the permeated water of the first membrane separation unit 14 discharged from the first permeated water discharge pipe 22, and the broken line shows that it is discharged from the second permeated water discharge pipe 24 in Fig. 5 - 39 - 201235090. The permeated water of the membrane separation unit 18 of the second. According to the measurement data of the first embodiment (Fig. 4), the measurement data of the sixth embodiment (Fig. 5), the recovery device 1 of the honing agent of the first embodiment (the first embodiment), and the honing of the embodiment 6 were designed and manufactured. Charge recovery device 11 (second embodiment). In the honing agent recovery device 1 1 of the second embodiment, the honing agent recovery device 1 of the first embodiment can be produced by reducing the number of use of the 87% hollow UF film module. As a result, it is possible to obtain a simplified structure of the piping as a whole of the recovery apparatus, and to reduce the installation area and reduce the cost. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A schematic structural view showing a recovery device for a honing agent according to an embodiment of the present invention. [Fig. 2] A view showing a cross section of a hollow system constituting one of the separation membranes 41. Fig. 3 is a schematic structural view showing a recovery device for a honing agent according to an embodiment of the present invention. Fig. 4 is a graph showing the relationship between the concentration of the honing agent in the processing container tank and the amount of permeated water discharged from the permeated water discharge pipe. [Fig. 5] shows the relationship between the concentration of the honing agent in the processing container tank 13 and the amount of permeated water discharged from the first permeated water discharge pipe 22 in the recovery apparatus of Fig. 3, and the enthalpy in the processing container tank 17. The concentration of the abrasive and the amount of permeated water discharged from the second to 40-201235090 through the water discharge pipe 24 [Fig. 6] show a photograph of f at the point when the separation membrane is closed. [Fig. 7] An enlarged photograph of Fig. 6. [Fig. 8] A photograph showing f at the point when the separation membrane is occluded. [Explanation of main component symbols] 1. 1 1 : Recovery device for honing agent 3 : Processing container tank 41 : Separation membrane 4 1 0S : Effective inner diameter 4 1 2 : Crossing surface 7 : Permeating water outlet piping 9 : Concentrated water Recycling container tank 1 3 : Front processing container tank 141 : First separation membrane 15 to 1 7 : Rear processing container tank 181 : Second separation membrane 22 : First permeated water outlet pipe 24 : Second permeated water outlet pipe 25 : 26 : Reflow piping C 1~C3 : The relationship diagram of the component concentration meter (flux). I state 2, 12 of the state separation unit outlet of the inlet of the separation unit: Protective filter 4: Membrane separation unit 410: Hollow system 41 1 : Support layer 5 to 6 : Pipe 8 : Concentrated water outlet pipe 1 0 : Reflow pipe 1 4 : First membrane separation unit 1 6 , 20 to 2 1 : Pipe U : 2nd membrane separation unit 1 9 : Recovery container tank 2 3 : Reflow piping concentrated water outlet pipe p 1 to P 3 : Pump opening and closing valve - 41 -