.1306841 九、發明說明： 【發明所屬技術領域】 . 本發明係關於高濃度微粒濃縮物、高濃度微粒濃縮物 製造方法、粉末及粉末製造方法。 【先前技術】 半導體製造中使用的矽基板及晶片等薄基板，採用 CMP(化學機械研磨）系統進行研磨使平坦化。一般的 系統，由於在半導體裝置製造步驟中實施曝光的層可完全 •平坦化，减輕了曝光技術的負擔，使產品合格率穩定，所 以，是進行層間絕緣膜、BPSG膜平坦化、軟吹.溝槽隔 離分離等時必需的技術。 在半導體裝置製造步驟中，作為電漿CVD(Chemicai -VaP〇r Deposition、化學蒸鍍法）、低壓_CVD等方法形成的 .二氧化矽絕緣膜等無機絕緣膜層進行平坦化時的CMp研 磨劑，以採用例如氧化鈽（Ce〇2)、二氧化矽粒子、氧化鋁 •粒子、二氧化鈦（Ti〇2)粒子等為較佳。另外，上述研磨劑， 通吊分散在水等溶劑中，進一步地，把適當的氯氧化卸等 化學反應催化劑或有機高分子或表面活性劑等分散劑添加 至該分散液中，形成研磨漿液。 採在該CMP系統中，藉由保持構件，採於載體片或 壓力板與可旋轉的研磨台或以壓板支承的研磨頭之間配置 基板（例如，半導體晶片）並進行研磨。在研磨頭上，即使 基板與研磨頭表面密接時，上述研磨聚液仍可供給達到基 板的中央部分，並於該表面形成細小的溝，在研磨期間， 316920 5 1306841 上述研磨漿液可用泵等連續供給至研磨頭。 採用該CMP系統，可以消除Si〇2絕緣膜表面的凹凸， 在全部半導體基板上形成平滑的面。 下面對半導體基板上的Si〇2絕緣膜層的CMP加以說 月但不限於此，具有規定配線的配線板、玻璃、氮化矽 等無機絕緣膜；光學掩模.透鏡.棱鏡等光學玻璃、IT0(氧 2銦錫)等無機導電膜;用玻璃及晶體材料構成的光學集成 :路光子轉換元件·光導波路、光學纖維端面、間燦器 I等光學用單晶；固體激光單晶、藍色激光用LED藍寶石基 板、Sic、Gap、GaAs等半導體單晶；磁盤用玻璃基板、 磁頭等都可採用CMP研磨。 上述CMP系統中排出的CMp廢水，例如含有研磨劑 使用的氧化㈣子、二氧切粒子、氧化銘粒子、二氧 鈦粒子及經研磨的金屬化合物微粒等有用的金屬化合物 用 因此’希望回收這些有用的金屬化合物微粒加以再利 屬化’例如採用過遽㈣⑽廢水中所含的金 萄化合物微粒加以道输& # 的妒窨可脾一 4、、的裝置已經開發出來。採用該從前 排水中的微粒濃縮至1 〇〇〇至5000mg/L。 然而，這種濃縮度的微粒難以再利用。 :别是最近開發出的過濾裳置“s一 ci〇 ，如’曰本特開2购職號公報)，係在孔厶25 # m過滹膜熹而祀、t7 丁你扎仕m 表㈣成凝膠過㈣，㈣泵抽吸職膜内之 316920 6 1306841 式;膜表面之洗淨僅產生輕微的空氣泡。採用該 ^慮虞置，例如可將微粒濃縮至1萬至30萬毫克/ /辰縮效率顯著提高。 升 希望k尚該尚濃縮微粒漿液的附加價值。 【發明内容】 ^明的目的在於謀求使廢水中回收的微粒附加值增 大，進一步提高循環使用周期。 曰 本發明有以下特徵。 (1) 一種高濃度微粒濃縮物，係由PH調整至3 的含低濃度微粒的溶液濃縮成含有1重量％至5G 粒的含高濃度微粒漿液而成。 〇 上述高濃度微粒濃縮物，可直接在各領域中使用，另 外’由於高濃縮’即使進行乾燥（水分調節）也 短 間得到所希望的粉末。 用紐時1.1306841 IX. Description of the Invention: [Technical Field] The present invention relates to a high-concentration microparticle concentrate, a method for producing a high-concentration microparticle concentrate, a powder, and a method for producing a powder. [Prior Art] A thin substrate such as a germanium substrate or a wafer used in semiconductor manufacturing is polished by a CMP (Chemical Mechanical Polishing) system to be planarized. In a general system, since the layer subjected to exposure in the semiconductor device manufacturing step can be completely and flattened, the burden on the exposure technology is reduced, and the yield of the product is stabilized, so that the interlayer insulating film, the BPSG film is flattened, and the soft blowing is performed. A technique necessary for trench isolation and the like. In the semiconductor device manufacturing step, the inorganic insulating film layer such as a cerium oxide insulating film formed by plasma CVD (Chemicai-VaP〇r Deposition, chemical vapor deposition) or low-pressure CVD is planarized by CMp polishing. The agent is preferably, for example, cerium oxide (Ce〇2), cerium oxide particles, alumina particles, titanium dioxide (Ti 2 ) particles or the like. Further, the above-mentioned polishing agent is dispersed in a solvent such as water, and further, a chemical reaction catalyst such as chlorine oxidative desorption or a dispersing agent such as an organic polymer or a surfactant is added to the dispersion to form a polishing slurry. In the CMP system, a substrate (e.g., a semiconductor wafer) is disposed between a carrier sheet or a pressure plate and a rotatable polishing table or a polishing head supported by a platen by a holding member and is ground. On the polishing head, even if the substrate is in close contact with the surface of the polishing head, the polishing liquid can be supplied to the central portion of the substrate, and a fine groove is formed on the surface. During the polishing, the slurry can be continuously supplied by a pump or the like during the polishing process. To the grinding head. According to this CMP system, irregularities on the surface of the Si〇2 insulating film can be eliminated, and a smooth surface can be formed on all the semiconductor substrates. In the following, the CMP of the Si〇2 insulating film layer on the semiconductor substrate is not limited thereto, and an insulating film such as a wiring board, a glass, or a tantalum nitride having a predetermined wiring; an optical glass such as an optical mask, a lens, and a prism is provided. Inorganic conductive film such as IT0 (oxygen 2 indium tin); optical integration composed of glass and crystal material: optical photo-transformation element, optical waveguide, optical fiber end face, optical single crystal such as inter-cancer I; solid-state laser single crystal, A blue laser LED sapphire substrate, a semiconductor single crystal such as Sic, Gap, or GaAs; a glass substrate for a magnetic disk, a magnetic head, or the like can be CMP-polished. The CMp wastewater discharged from the CMP system, for example, contains a useful metal compound such as an oxidized (tetra), an oxidized particle, an oxidized particle, a titanium dioxide particle, and a ground metal compound fine particle used for an abrasive. The useful metal compound microparticles are re-ligregated, for example, a device using a glucosinolate microparticle contained in the wastewater of 遽(4)(10), and a spleen spleen 4 has been developed. The particles in the previous drainage are concentrated to 1 〇〇〇 to 5000 mg/L. However, such concentrated particles are difficult to reuse. : Don't be the recently developed filter skirt "s a ci〇, such as '曰本特开2购职号 bulletin'), attached to the hole 25# m over the membrane and 祀, t7 丁你扎仕m表(4) gelation (4), (4) pumping 316920 6 1306841 type in the membrane; washing of the membrane surface only produces a slight air bubble. With this device, for example, the particles can be concentrated to 10,000 to 300,000 The milligram//shrinking efficiency is remarkably improved. The desired value of the still-concentrated microparticle slurry is as follows. [Explanation] The purpose of the invention is to increase the added value of the particles recovered in the wastewater and further improve the cycle of use. The present invention has the following features: (1) A high-concentration fine particle concentrate obtained by concentrating a solution containing a low concentration of fine particles having a pH adjusted to 3 into a slurry containing a high concentration of fine particles containing 1% by weight to 5G particles. The concentration of the fine particle concentrate can be directly used in various fields, and the desired powder can be obtained in a short period of time due to high concentration (moisture adjustment).
(2) —種南濃度微粒濃縮物製造方法，包含將pH調整 至3至8的含低濃度微粒的溶液濃縮成含有1重量％至 重里％微粒的含高濃度微粒漿液。 〃上述同樣的兩》辰度微粒濃縮物，可直接在各領域中 使用，另外，由於高漠縮，即使進行乾燥（水分調節^ 以用短時間得到所希望的粉末。 古曲⑺-種製造粉末的方法，纟中，把上述⑴中所述的 尚，度微粒濃縮物’即含上述高濃度微粒的漿液，再根攄 ，燥後所得到的粉末粒徑’於再分散時調整含微粒漿液乂的 濃度’然後進行乾燥（水分調節）。 316920 7 ^06841 將含南濃度微粒的漿液 M , x 根據乾焯後所得到的格± 优，於再分散時調整 ，付A的杨末粒 分销J ;水液之;辰度，然後進行乾 刀調即），可以得到所希望 W仃乾屎(水 末。 ^、、帝〇狀怨，即所需要粒徑的粉 (4) 一種製造粉末的方法，1 含高濃戶;八中把上述（2)中所述的 再分根據乾燥後所得到的粉末粒徑，於 ::㈣含微粒的聚液濃度，然後進行乾燥。 得到的粉末粒徑，於再分…：：:K液’根據乾燥後所 進行㈣u、 再刀政Η調整U粒漿液之濃度，然後 丁乾知（水为調節），可以得到 希望粒徑的粉末。 帀呈的締合狀態，即所 有種粉末製造方法，包含將仲調整至3至8的含 生成粉至Μ重量％微粒㈣液進行真空冷束乾燥，(2) A method for producing a southern concentration fine particle concentrate comprising concentrating a solution containing a low concentration of fine particles having a pH adjusted to 3 to 8 into a slurry containing a high concentration of fine particles containing 1% by weight to 3% by weight of the fine particles. 〃The same two "fine particle concentrates" can be used directly in various fields. In addition, due to high shrinkage, even drying (moisture adjustment ^ to obtain the desired powder in a short time. Guqu (7) - Seed manufacturing In the method of powder, the fine particle concentrate of the above-mentioned (1), that is, the slurry containing the high-concentration fine particles, is further kneaded, and the particle size of the powder obtained after drying is adjusted to contain particles during redispersion. The concentration of the slurry ' is then dried (moisture adjustment). 316920 7 ^06841 The slurry M containing the concentration of the south concentration is adjusted according to the lattice obtained after the drying, and is adjusted during the redispersion. Distribution J; water liquid; Chen, then dry knife adjustment), you can get the desired W仃 dry (water end. ^,, emperor, resentment, that is, the required particle size of the powder (4) a manufacturing The method of powder, 1 contains a high-concentration; the eighth is divided into the above-mentioned (2) according to the particle size of the powder obtained after drying, at: (4) the concentration of the liquid containing the particles, and then dried. Powder particle size, after sub-dividing ...:::K liquid 'based on drying Carry out (4) u, then knife and sputum to adjust the concentration of U-grain slurry, and then Ding Qianzhi (water is adjusted), you can get the powder of the desired particle size. The association state of 帀, that is, all kinds of powder manufacturing methods, including the adjustment of the secondary Up to 3 to 8 containing the powder of the generated powder to the weight % of the fine particles (four) for vacuum cold drying,
^於以高濃度粉末㈣液進行真空冷;東乾燥，故可以 液高的粉末。 叫’可以传到附加價值比漿 ’其中該微粒的平 (6)上述（1)所述的高濃度微粒濃縮物 均粒徑為50nm至500nm。 (7) 上述（2)所述的高濃度微粒濃縮物的製造方法，其 中該微粒的平均粒徑為5〇nm至5〇〇nm。 /、 (8) 上述⑶、（4)、（5)中任—項所述的粉末製造方法， 其中，該微粒的平均粒徑為5〇nm至5〇〇nm。 (9) 在上述（1)所述的高濃度微粒濃縮物中，含有低濃 316920 8 1306841 度微粒的溶液為CMP廢水。 (10) 在上述(2)所述的高濃度微粒濃縮物的製造方法 中’含有低濃度微粒的溶液為CMP廢水。 (11) 在上述⑴或⑹所述的高濃度微粒濃縮物中，該 微粒至少含有Si02。 、（12)在上述⑺或⑺所述的高濃度微粒濃縮物的製造 方法中，該微粒至少含有Si〇2。 、（13)在上迹⑺、（4)、（5)中任—項所述的粉末製造方 法中，該微粒至少含有Si〇2。 由於上述是在廣泛的領域中作為試劑之有用物 質，故製成粉末可得到增大之附加價值。 (14)在上述⑴所述的高濃度微粒濃縮物中，含有低濃 度微粒的溶液係經由酸性CMp廢水和驗性cMp廢水混 合，並調至pH3至8而成。 (15)在上述⑺所述的高濃度微粒濃縮物的製造方法 中，含有低濃度微粒的溶液係經由酸性 CMP廢水混合’並將阳調整至…而成。 驗丨生 上述〇)或⑹所述的高濃度微粒濃縮物中，微 粒：少含有Sl02、氧化飾、氧化銘、二氧化鈦、金屬氣氧 化物、氧化物、陶莞，、氫氧化鐵或氟化舞。 乳 ⑼在上述（2)或⑺所述的高濃度微粒濃 方法中’微粒至少含有吨、氧化鈽、氧㈣、二氧化Γ 金屬虱乳化物、氧化物、陶究，、氫 ⑽在上述㈣W5)中任一項所述的：方 316920 9 1306841 上述微粒至少含有Si〇2、氧化鈽、氧化鋁、一 法中， 氧化 、氫氧化鐵或氟化 太金屬氫氧化物、氧化物、陶瓷、銦 鈣。 上述微粒均為有用的金屬化合物，希望回收再利用。 (19) 在上述（5)所料粉末製造^巾， 合有Si02、氧化飾、氧化紹或二氧化鈦。 :列:’可將下述CMP廢水中所含的上述S102、氧化 ，节軋化銘、二氧化鈦製成料廣泛、附加價值高的粉末。 (20) 在上述(3)'(4)、(5)、(8)、(13) (18)、 一 員所述的粉末製造方法中，所得到的粉末比表 l〇m2/g 至 4〇〇 m2/g。 經由乾燥，可使所得粉末比表面積增大。進而，經由 ，支更乾燥條件’可將所得粉末比表面能财合適的程度。 ⑼-種粉末’其特徵在於由上述（5)、⑻、⑽、 (19)、㈣中任—項所述的粉末製造方法得到且該粉末的平 均粒徑為5 /z m至1 〇〇 # m。 (22) —種粉末，係由上述⑺、（4)、⑻、（⑶、（^)、 (19)、（2G)巾任-項所述的粉末製造方法得到。 按照本發明’可以得到能循環再利用的高濃度毁液及 比該漿液附加值高的粉末。 【實施方式】 下面說明本發明的較佳實施方案。 士第1圖表示本發明的粉末製造方法中使用的粉末製造 裝置結構。如第i圖所^，本實财案_末製造裝置大 316920 1306841 致構成為：處理上述CMP(化學機械研磨）廢水的過濾裝置 10;以及將經由該過濾裝置10濃縮至高濃度，例如丨重量 %至50重量％，優選（以20重量％至5〇重量％為較佳）的漿 液進行真空冷凍乾燥的真空冷凍乾燥器20。並且，在過濾 農置1G内’ 上所述，¥孔徑G.25//m的過濾、膜表面設 ，置膜組件12’該組件中安裝至少1片或1片以上的形成凝 膠層的寒膠過濾膜。另外，用泵14從膜組件12的凝膠過 濾膜内抽吸廢水。上述過濾裝置1〇,以例如在膜表面僅產 •生輕微氣泡的“Slurry Cl〇sei”(商品名)(三洋水技術公司製) 為較佳 /作為上述CMP廢水中的微粒，例如，可以舉出CMp 系統中使用的研磨劑，例如氧化鈽（Ce〇2)、二氧化矽粒子、 氧化鋁粒子、一氧化鈦（BO2)粒子等，這些研磨劑微粒是 CMP廢水中的主要成分，另夕卜還含有作為半導體基板的 si〇2絕緣膜層研磨屑的Si〇2粒子或金屬氫氧化物、氧化 I物、陶瓷、銦、氫氧化鐵、氟化鈣等。 特別是，半導體基板的Si02絕緣膜層，採用由二氧化 矽粒子構成的研磨劑進行研磨時產生的CMP廢水，由於 其pH接近10，故被稱作鹼性CMp廢水’該鹼性cMp廢 水，其CMP廢水中的無機微粒幾乎1〇〇%是Si〇〆。而且， 作為CMP廢水，上述鹼性CMp廢水所占的比例大。另一 方面，在半導體領域或其他領域中進行研磨時而產生的， 且含有很多除si〇2以外的金屬的CMP廢水，由於其 接近2，故被稱作酸性CMP廢水。 316920 11 1306841 這種CMP廢水中微粒的平均粒徑為5〇nm至5〇〇nm， 處於稱作膠^的粒徑範圍，優選5〇1^至2〇〇nm，通常多 數在lOOnm附近。例如，當微粒為Si〇2時，呈膠體二氧 化矽狀態。 供給上述過濾裝置10的含低濃度微粒的溶液，特別是 CMP廢水的pH調整至3至8者是優選的。如第2圖所示， 在含無機微粒為1GG%S办的低濃度溶液中，在pH4附近 的比表面積最高’豸pH為等電點。另外，採用上述粉末 衣造裝置進行濃縮·真空冷;東乾燥後的Si〇2的粉末比表面 積’，作為高效能粒子可使用的比表面料u〇m2/g或 ^化以上，希望邱在8或8以下。另一方面當含低 :度微粒的溶液pH小於3時，比表面積不僅减少，而且， 也慮裝置中進行湲縮處理時有時會發生腐钱，因而不 另外’對於含㈣度㈣的溶液pH •产東= 麦的粉末比表面積的關係，以僅含Si〇2 — 度洛液為例’用第3圖至第5圖加以詳細說明。_ =3圖所示’含Sl〇2微粒的溶液pH比等電 的帶電粒子溶液，，)’經由微粒表面 〜▼免桩子間排斥力的作用， 以凝聚，比表面積有變小的傾白：：㈣’結果是難 告人ς.π心 的傾向。另外’如第4圖所示， q s1〇2微粒的溶液ρΗ比等電點ρΗ4大 廷裡稱作“鹼性溶液，，），經由 、4時（在 的作用，枱；鬥 、'由微粒表面的帶電粒子間排斥力 粒子間距離拉開，結果是難以凝聚’比表面積有 316920 12 .1306841^It is vacuum-cooled with a high-concentration powder (tetra) solution; it is dried in the east, so it can be a liquid powder. The average concentration of the high-concentration microparticle concentrate described in the above (1) is 50 nm to 500 nm. (7) The method for producing a high-concentration fine particle concentrate according to the above (2), wherein the fine particles have an average particle diameter of from 5 Å to 5 Å. (8) The method for producing a powder according to any one of (3), wherein the fine particles have an average particle diameter of from 5 Å to 5 Å. (9) In the high-concentration fine particle concentrate described in the above (1), the solution containing the low-concentration 316920 8 1306841 particles is CMP wastewater. (10) In the method for producing a high-concentration fine particle concentrate according to the above (2), the solution containing the low-concentration fine particles is CMP wastewater. (11) In the high-concentration fine particle concentrate according to (1) or (6) above, the fine particles contain at least SiO 2 . (12) The method for producing a high-concentration fine particle concentrate according to the above (7) or (7), wherein the fine particles contain at least Si〇2. (13) In the method for producing a powder according to any one of the above items (7), (4), (5), the fine particles contain at least Si〇2. Since the above is a useful substance as a reagent in a wide range of fields, the added value of the powder can be obtained. (14) The high-concentration fine particle concentrate according to the above (1), wherein the solution containing the low-concentration fine particles is mixed with the acidic CMp wastewater and the testable cMp wastewater, and adjusted to a pH of 3 to 8. (15) The method for producing a high-concentration fine particle concentrate according to the above (7), wherein the solution containing the low-concentration fine particles is mixed with the acidic CMP wastewater and adjusted to a temperature of . In the high concentration microparticle concentrate described in the above 〇) or (6), the microparticles contain less S102, oxidized, oxidized, titanium dioxide, metal oxide, oxide, ceram, iron hydroxide or fluorinated. dance. The milk (9) in the high concentration fine particle concentration method according to the above (2) or (7), wherein the fine particles contain at least tons, cerium oxide, oxygen (tetra), cerium oxide metal lanthanum emulsion, oxide, ceramics, hydrogen (10) in the above (four) W5 Any one of the following: square 316920 9 1306841 The above-mentioned fine particles contain at least Si 〇 2, cerium oxide, aluminum oxide, one method, oxidation, iron hydroxide or fluorinated too long metal hydroxide, oxide, ceramic, Indium calcium. The above-mentioned fine particles are all useful metal compounds, and it is desirable to recycle them. (19) The powder produced in the above (5) is prepared by combining SiO 2 , oxidizing, oxidizing or titanium dioxide. : Column: 'The above-mentioned S102, oxidized, calcined, and titanium dioxide contained in the CMP wastewater can be made into a wide range of powders with high added value. (20) In the powder production method according to the above (3) '(4), (5), (8), (13), (18), and one of the members, the obtained powder has a ratio of l〇m2/g to 4 〇〇m2/g. The resulting powder can be increased in specific surface area by drying. Further, the obtained powder can be made more suitable than the surface by the drying condition. (9) A powder which is obtained by the method for producing a powder according to any one of the above (5), (8), (10), (19), (4), and the average particle diameter of the powder is 5 /zm to 1 〇〇# m. (22) A powder obtained by the method for producing a powder according to the above (7), (4), (8), ((3), (^), (19), (2G) towel, or the like. A high-concentration decomposing liquid capable of recycling and a powder having a higher added value than the slurry. [Embodiment] Hereinafter, a preferred embodiment of the present invention will be described. Fig. 1 is a view showing a powder producing apparatus used in the powder producing method of the present invention. The structure of the present invention is as follows: the present invention, the final manufacturing apparatus 316920 1306841, is configured as: a filtering device 10 for treating the above CMP (Chemical Mechanical Polishing) wastewater; and will be concentrated to a high concentration via the filtering device 10, for example A vacuum freeze-drying vacuum freeze dryer 20 is preferably subjected to vacuum freeze-drying of a slurry having a weight of 5% by weight to 50% by weight, preferably (20% by weight to 5% by weight), and is described in "Filtering Agricultural 1G" The filtration of the pore size G.25/m, the surface of the membrane, and the membrane assembly 12' are provided with at least one or more gel filtration membranes forming a gel layer. Further, the membrane assembly 12 is pumped from the membrane module 12. Pumping wastewater into the gel filtration membrane. For example, "Slurry Cl〇sei" (trade name) (manufactured by Sanyo Water Technology Co., Ltd.) which produces only a slight bubble on the surface of the film is preferably/as a fine particle in the above CMP wastewater, and for example, Abrasives used in CMp systems, such as cerium oxide (Ce〇2), cerium oxide particles, alumina particles, titanium oxide (BO2) particles, etc. These abrasive particles are the main components in CMP wastewater. Further, it contains Si〇2 particles, metal hydroxide, oxidized material, ceramic, indium, iron hydroxide, calcium fluoride, etc., which are Si〇2 insulating film layer polishing chips as a semiconductor substrate. In particular, SiO2 insulation of a semiconductor substrate The film layer, which is produced by grinding with an abrasive composed of cerium oxide particles, has a pH close to 10, so it is called alkaline CMp wastewater, which is an alkaline cMp wastewater, and the inorganic particles in the CMP wastewater are almost 1〇〇% is Si〇〆. Moreover, as the CMP wastewater, the above-mentioned alkaline CMp wastewater accounts for a large proportion. On the other hand, it is produced in the semiconductor field or other fields, and contains many Metal other than 2 CMP wastewater is called acidic CMP wastewater because it is close to 2. 316920 11 1306841 The average particle size of the particles in the CMP wastewater is 5 〇 nm to 5 〇〇 nm, which is in the particle size range called gel. 5 〇 1 ^ to 2 〇〇 nm, usually in the vicinity of 100 nm. For example, when the particles are Si 〇 2, it is in the state of colloidal cerium oxide. The solution containing the low concentration of particles supplied to the above filtering device 10, especially CMP wastewater The pH is adjusted to 3 to 8. As shown in Fig. 2, in the low concentration solution containing inorganic particles of 1 GG%, the specific surface area near pH 4 is the highest '豸pH is the isoelectric point. In addition, the powder coating apparatus is used for concentration and vacuum cooling; the powder specific surface area of Si〇2 after the east drying is used as a specific surface material u〇m2/g or more than high-performance particles, and it is hoped that Qiu 8 or less. On the other hand, when the pH of the solution containing the low-particles is less than 3, the specific surface area is not only reduced, but also the rot is sometimes caused when the tamping process is performed in the apparatus, so that there is no other solution for the (four) degree (four). pH • The relationship between the specific surface area of the powder of the east and the wheat is described in detail in the figure of Fig. 3 to Fig. 5 with the case of containing only Si〇2 - Duluo liquid. _ =3 shows the solution of the solution containing the S1〇2 particles at a lower pH than the charged particles of the isoelectric charge, and the effect of the repulsive force between the piles via the surface of the particles to avoid condensation, and the specific surface area becomes smaller. :: (4) 'The result is a tendency to confess. 心 heart. In addition, as shown in Fig. 4, the solution of q s1 〇 2 particles ρ Η is equal to the isoelectric point ρ Η 4 is called "alkaline solution,", via 4, (in the role of the table; bucket, 'by The repulsive force between charged particles on the surface of the particles is separated by the distance between the particles, and as a result, it is difficult to agglomerate 'the specific surface area is 316920 12 .1306841
， 變小的傾向。另外，L哲C ” 如第5圖所示’當含Si02微粒的溶液 • 電點PH 4時（在這裏稱作“中性溶液”），由於微粒 +帶電’粒子間不發生排斥作用，粒子間距離接近， •粒子易於凝聚，結果是比表面積加大。 .作為上述含低濃度微粒的溶液pH調整方法，可以舉 入（。）把述CMp廢水和驗性CMp廢水加以適當混 °可以°周整至pH3至8。（b)向酸性及/或鹼性CMP廢水 中添=PH調節劑’可以配製經過阳調節後的含低漠度微 •的/合^在這裏’作& PH調節劑，例如可以採用氫氧 H、氫氧^等。作為其他方案，⑷向上述過滤裝置10 七、給未調喊pH的含低濃度微粒的溶液後，可以用上述 _ p H一調^劑適當調節上述過遽裝置1 〇中的P Η。另外，作為 另一貫施方案，（d)把含有未調整過ΡΗ的低濃度微粒溶液 .供給上述過濾裳置1〇’在該過遽裝置1〇内邊監測阳邊在 PH超出3至8的範圍時使該濃縮處理終止，可以作為含有 %高濃度微粒的漿液。 在本實施方案中，CMP廢水，特佳為將以Si〇2微粒 為主體的鹼性CMP廢水的pH加以調整，進行濃縮·真空 冷凍乾燥而成者。在這種情况下，由於可以得到純度高的 純Si〇2粉末’故可再用作高附加值粉末。 * a另外’用上述過濾裝置10將上述含低濃度微粒的溶液 濃縮至高濃度，以！重量％至5〇重量％為較佳，以濃縮至 2〇胃重量％至50重量％的漿液為更佳。特別是將濃縮至2〇 重量％至50重量％的高濃度的漿液進行真空冷凍乾燥，可 316920 13 1306841 以大幅縮短乾燥時間，另外，可 在本實施方案中， -=呆持所得粉末的粒徑。 r' 的乾燥ϋ，^含高濃度微粒的漿液 絲时^縣用真空冷;東乾燥器μ 燥的條件，可根據含高濃度 為>、二7凍乾 如在至。。c，㈣;度:5=:農度適編^ (冰溫）為更佳，直空度以2 S S為1^佳、以-10°c至-5°c 為較佳。作為真空冷凌乾至6.7hpa(N/m2)) “TFD-550-8SP”（寶酒公司製）。 歹1J如’可以採用 按/本發明人的實驗，採 3〇重！%的漿液中的微粒平均 ： ^東=*進㈣碎，其粉末的平均粒徑為 另-方面，當對該聚液進行加熱 ： 體故用研缽進仃粉碎。該粉碎過的 心。因此，在想要得到粒徑 ”立一“120.8 燥為較佳。 U的私末日夺’以實施冷康乾, the tendency to become smaller. In addition, L Zhe C ′′ as shown in Fig. 5 'When the solution containing SiO 2 particles • the electric point PH 4 (herein referred to as “neutral solution”), the particles do not repel between particles + charged particles, particles The distance between the particles is close, and the particles tend to aggregate, resulting in an increase in the specific surface area. As a method for adjusting the pH of the solution containing the low-concentration particles, it is possible to appropriately mix the CMp wastewater and the CMp wastewater. Weekly to pH 3 to 8. (b) Adding a pH regulator to the acidic and/or alkaline CMP wastewater' can be formulated with a low-intensity micro-integrated/supplemented here. As the regulator, for example, hydrogen oxyhydrogen H, hydrogen oxyhydroxide, etc. may be used. (4) To the above-mentioned filtration device 10, after a solution containing a low concentration of fine particles which is not pH-adjusted, the above-mentioned _p H may be used. The agent appropriately adjusts the P Η in the above-mentioned sputum device 1 Η. In addition, as another embodiment, (d) the low-concentration microparticle solution containing the unadjusted ruthenium is supplied to the filter skirt 1 〇' 1〇Inside monitoring of the positive side makes the concentration when the pH exceeds the range of 3 to 8. In the present embodiment, the CMP wastewater is preferably adjusted to have a pH of the alkaline CMP wastewater mainly composed of Si 2 particles, and is concentrated and vacuum freeze-dried. In this case, since a pure Si〇2 powder having a high purity can be obtained, it can be reused as a high value-added powder. * a Further, the above-mentioned filter device 10 is used to concentrate the above solution containing a low concentration of particles to a high level. The concentration is preferably from 5% by weight to 5% by weight, more preferably from 2% by weight to 50% by weight of the slurry. In particular, it is concentrated to a high concentration of from 2% by weight to 50% by weight. The slurry is vacuum freeze-dried to 316920 13 1306841 to greatly shorten the drying time. In addition, in the present embodiment, -= the particle size of the obtained powder is retained. The dry ϋ of r', the slurry containing high concentration of particles ^ County vacuum cooling; East dryer μ dry conditions, can be based on high concentration of >, 2, 7 freeze-dried as in. c, (four); degree: 5 =: agricultural degree suitable ^ (ice temperature) For better, the straight space is 2 SS for 1^, and -10°c to -5°c. Preferably, it is vacuum-cooled to 6.7 hpa (N/m2)) "TFD-550-8SP" (manufactured by Takara Co., Ltd.). 歹1J can be used according to the experiment of the inventor. The average particle size in the % slurry: ^ East = * into (four) broken, the average particle size of the powder is another - aspect, when the poly liquid is heated: the body is crushed with a mortar. The crushed heart. Therefore, in order to obtain the particle size "立一" 120.8 dry is better. U's private end of the day' to implement cold Kanggan
高噥上述過濾裝i 1〇得到的高濃度微粒濃縮物的 间/辰度漿液，既可以直接佶田 n u,,, 也可以用作陶兗的瓷釉、 妝材科、研磨劑。另外，可根 的濃縮物中添加適當的其他添加劑。 这门辰度破粒 乾燁造裝置’在上述條件Τ進行真空冷凌 ::2時，可以得到平均粒徑約3。㈣的粉末，即孰 解一乳化石夕（fumed silica)。 另外’把根據上述過遽裝置1〇得到的含高濃度微粒裝 316920 14 1306841The sorghum slurry of the high-concentration microparticle concentrate obtained by the sorghum filter can be directly used as the enamel, the cosmetic enamel, and the abrasive. In addition, suitable other additives are added to the root concentrate. The granules of the granules of the dry granules were subjected to vacuum cold chilling ::2 under the above conditions, and an average particle diameter of about 3 was obtained. (4) The powder, that is, fumed silica. In addition, the high-concentration particles obtained according to the above-mentioned passing device 1 316920 14 1306841
Si〇2粉末比表面積之關係圖。 第3圖係顯示酸性、含低濃度Si〇2微粒之溶液中 微粒的表面狀態之模式圖。 2 第4圖係鹼性、含有低濃度Si〇2微粒之溶液中Si〇2 微粒的表面狀態之模式圖。 ^第5圖係Sl〇2等電點附近的含有低濃度Si02微粒之 溶液中Si〇2微粒的表面狀態之模式圖。 【主要元件符號說明】 • 1〇過遽裝置 Π膜組件 14 yG 1 c 汞 16 傳送泵 20 真空冷凍乾燥裝置Diagram of the specific surface area of Si〇2 powder. Fig. 3 is a schematic view showing the surface state of fine particles in a solution containing acidic, low-concentration Si〇2 fine particles. 2 Fig. 4 is a schematic view showing the surface state of Si〇2 particles in a solution containing alkaline and low-concentration Si〇2 particles. Fig. 5 is a schematic view showing the surface state of Si 〇 2 fine particles in a solution containing a low concentration of SiO 2 particles in the vicinity of the isoelectric point of Sl 〇 2 . [Main component symbol description] • 1〇 〇 device Π membrane module 14 yG 1 c mercury 16 transfer pump 20 vacuum freeze-drying device
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