，200538404 • 九、發明說明： 【發明所屬技術領域】 , 纟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秒基板及晶片等薄基板，採用 ⑽P(化學機械研磨）系統進行研磨使平坦化。—般的⑽ 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財坦化、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，作為電冑CVD(chemlcal V—P〇sltlon、化學蒸鍵法）、低壓_cVD等方法形成的 -乳化我緣膜等無機絕緣膜層進行平坦化時的CM 磨劑，以採用例如氧化飾（Ce02)、二氧化石夕粒子 _粒:、二氧化鈦（加2)粒子料較佳。另外，上述研磨劑， ::::在水等溶劑中，進一步地，把適當的氫氧化卸等 劑或有機高分子或表面活性劑等分散劑添加 至4刀放液中，形成研磨漿液。 A在.玄CMP π、統中’藉由保持構件，採於 壓力板與可旋轉的研磨台或以壓板支承的研磨頭之間配^ =反^如，半導體晶片）並進行研磨。在研磨頭上，即使 研磨頭表面密接時，上述研磨漿液仍可供給達到基 、中央部分，並於該表面形成細小的溝，在研磨期間， 316920 .200538404 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吨絕賴層的⑽加以說 =’但不限於此’具有規定崎的喊板、玻璃、氮化石夕 寻無機絕緣膜；光學掩模.透鏡.棱鏡等光學玻璃、㈣(氧 化銦錫）寺無機導電膜；用玻璃及晶體材料構成的光學率成 ,電路··光，轉換元件.光導波路、光學纖維端面、閃燦器 等光予用單日日，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、 磁頭專都可採用CMP研磨。 上述CMP系統中排出的CMp廢水，例如含有研磨劑 中使用的氧化錦粒子、二氧切粒子、氧化|g粒子、二氧 化鈦粒子及經研磨的金屬化合物微粒等有用的金 微粒。 因此，希望回收這些有用的金屬化合物微粒加以再利 用。 近幾年來，例如採用過濾膜把CMp廢水中所含的金 屬化合物微粒加以濃縮的裝置已經開發出來。採用該從前 的裝置可將CMP排水中的微粒濃縮至i刪至5麵叫几。 然而’這種濃縮度的微粒難以再利用。 特别是最近開發出的過濾裝置“Slurry cl〇ser”（商品 名）(例如，日本特開2003_135914號公報），係在孔徑〇25 “過濾膜表面形成凝膠過濾膜，再用果抽吸過渡膜内之 316920 6 200538404 廢水的形式，膜表面之洗淨僅產生輕微 過遽裝置，例如可將微粒濃縮 十J : 6亥 濃縮效率顯著提高。 4至30“克/公升， 希望提高該高濃縮微粒漿液的附加價值。 【發明内容】 ' 大，：:：：：的在於謀求使廢水中回收的微粒附加值增 進 V提兩循環使用周期。 本發明有以下特徵。 ⑴種南濃度微粒濃縮物，係由調整至3 的含低濃度微粒的溶液濃縮成含 粒的含高濃度微粒漿液而成。 重"❶至5。重量%微 上述高濃度微粒濃縮物，可直接在各領域中使用 ，由於向濃縮，即使進行乾燥（水 間得到所希望的粉末。 也了以用紐時 至3 Ϊ)8:，農，粒濃縮物製造方法，包含將ΡΗ調整 曰 9 3低浪度微粒的溶液濃縮成含有】重量Q/ 重量％微粒的含高濃度微粒漿液。 〇 使用與ί:同樣的高濃度微粒濃縮物’可直接在各領域中 =外’由於高濃縮’即使進行乾燥（水分調也 以用紐日可間得到所希望的粉末。 可 (3)-種製造粉末的方法，其中，把上述⑴ 南濃度微粒濃縮物’即含上述高濃度微粒的漿液，再:攄 !燥後所得到的粉末粒徑’於再分散時調整含微教毁= /辰度，然後進行乾燥（水分調節）。 勺 316920 7 .200538404 將含高濃度微粒的漿液，根據乾燥後所得 控，於再分散時調整含微粒藥液之濃度，然後進n :調節)，可以得到所希望的締合狀態，即所需要粒徑:: 禋裂造粉末的方法 N 丁 八古、曲由心， …，化工现（2)中所述的 3…辰度雜勺聚液，根據乾燥後所得到的粉 再分散時調整含微粒的漿液漠度，然後進行乾燥。-於 1把與上述同樣的含高濃度微粒的聚液，根據乾 付到的粉末粒徑，於再分散時調整微粒漿液之濃度200538404 Nine, Description of the invention: [Technical field to which the invention belongs], The invention relates to high-concentration particulate concentrate, high-concentration particulate concentrate. Manufacturing method, powder and powder manufacturing method. [Prior art] Thin substrates such as second substrates and wafers used in semiconductor manufacturing are polished with a ⑽P (chemical mechanical polishing) system to flatten them. -General system, because the layer that is exposed in the semiconductor device manufacturing step can be completely flattened, reducing the burden of exposure technology, and stabilizing the yield rate of the product. Therefore, the interlayer insulation film, BPSG financialization, softening Blowing, trench isolation, and other necessary techniques. In the manufacturing process of semiconductor devices, it is used as a CM abrasive when planarizing inorganic insulating film layers such as emulsified rim films formed by methods such as electro-chemical CVD (chemlcal V-Posltlon, chemical vapor bonding method), and low pressure _cVD. It is preferred to use, for example, Ce02, SiO2 particles, and titanium dioxide (plus 2) particles. In addition, the above-mentioned abrasive, :::: is further added in a solvent such as water, and a suitable dispersant such as an hydroxide release agent or an organic polymer or a surfactant is added to the 4-knife discharge liquid to form a polishing slurry. A. In the Xuan CMP π system, through the holding member, it is collected between the pressure plate and a rotatable polishing table or a polishing head supported by the pressure plate, and is polished. On the grinding head, even when the surface of the grinding head is in close contact, the above-mentioned grinding slurry can still be supplied to the base and the central part, and a small groove is formed on the surface. During the grinding, the above-mentioned grinding slurry can be continuously supplied to the grinding head by a pump or the like. . With this CMP system, unevenness on the surface of the SiO2 insulating film can be eliminated, and a smooth surface can be formed on all semiconductor substrates. The following is the description of the ton of absolute layer on the semiconductor substrate = 'but not limited to this' has a predetermined squeegee plate, glass, nitride nitride insulation film; optical masks, lenses, prisms and other optical glass, ㈣ (Indium Tin Oxide) temple inorganic conductive film; optical components made of glass and crystal materials, circuits, light, conversion elements. Light guide wave path, optical fiber end face, flash light, etc., single-day, solid-state laser Single crystals, LED sapphire substrates for blue lasers, semiconductor single crystals such as SiC, GaP, GaAs; glass substrates for magnetic disks, and magnetic heads can be polished using CMP. The CMP wastewater discharged from the CMP system contains, for example, useful gold particles such as oxidized bromide particles, dioxon particles, oxidized particles, titanium dioxide particles, and ground metal compound particles used in abrasives. Therefore, it is desirable to recover these useful metal compound particles for reuse. In recent years, for example, a device for concentrating fine particles of metal compounds contained in CMP wastewater by using a filtration membrane has been developed. With the previous device, the particles in the CMP drainage can be concentrated to 5 sides. However, the particles having such a concentration are difficult to reuse. In particular, the recently developed filter device "Slurry close" (trade name) (for example, Japanese Patent Application Laid-Open No. 2003_135914) is formed on the surface of the pore size "25", and a gel filtration membrane is formed on the surface of the filtration membrane. In the form of 316920 6 200538404 wastewater in the membrane, the surface of the membrane is cleaned only to produce a slight dusting device. For example, it can concentrate particles. J: 6 Hai concentration efficiency is significantly improved. 4 to 30 "g / L, hope to improve the high concentration Added value of particulate slurry. [Summary of the invention] 'Big, :::::' seeks to increase the added value of particulates recovered in wastewater by increasing the V cycle for two cycles. The present invention has the following features. The Nagano concentration microparticle concentrate is made by concentrating a solution containing low concentration microparticles adjusted to 3 into a particle concentration-containing high concentration microparticle-containing slurry. Heavy " ❶ to 5. The above-mentioned high-concentration microparticle concentrate in weight% can be used directly in various fields. Since it is concentrated, it can be dried (the desired powder can be obtained between water. It can also be used from New Zealand to 3 Ϊ) 8: A method for producing a concentrate, which comprises concentrating a solution of the PJ-adjusted low-wave particle of 9 3 to a high-concentration particle-containing slurry containing [weight Q /% by weight of particles]. 〇Using the same high-density microparticle concentrates as the ί: can be directly used in various fields = outside 'due to high concentration' even if drying (moisture adjustment, the desired powder can be obtained in New Zealand.) A method for manufacturing a powder, in which the above-mentioned nannan fine particle concentrate 'that is, the slurry containing the above-mentioned high-concentration fine particles, and then: 摅! The particle size of the powder obtained after drying' is adjusted when redispersed = / Chen Duo, and then dry (moisture adjustment). Spoon 316920 7 .200538404 The slurry containing high concentration of particles, according to the control after drying, adjust the concentration of the drug solution containing particles during redispersion, and then enter n: adjust) To obtain the desired association state, that is, the required particle size :: Method for making powder by cracking N Ding Bagu, Qu Youxin,…, 3… Chendu miscellaneous liquid polymer described in Chemical Industry (2), The particle-containing slurry was adjusted for redispersion of the powder obtained after drying, and then dried. -Adjust the concentration of the particle slurry at the time of redispersion at a time when the polymer solution containing the high concentration of particles is the same as the above, according to the particle size of the dried powder.
=乾燥(水分調節)，可以得到所希望的締，即所 希望粒徑的粉末。 W (5卜種粉末製造方法’包含將pH調整至3至8的含 重#%至5G重量％微粒㈣液進行真空冷;東 生成粉末。 空冷凍乾燥，故可以 以得到附加價值比漿= Drying (moisture adjustment), a powder having a desired particle size can be obtained. W (5 kinds of powder manufacturing method 'includes adjusting the pH to 3 to 8 with a weight of #% to 5G% by weight of microparticles and mash to perform vacuum cooling; forming a powder. It can be freeze-dried in the air, so it can obtain additional value ratio slurry.
由於以南渡度粉末的漿液進行真 大Ί3田縮短粉末乾燥的時間，同時，可 液南的粉末。 物’其中該微粒的平 (6)上述（1)所述的高濃度微粒濃縮 均粒徑為50nm至5〇〇nm。 其 ⑺上述⑺所述的高濃度微粒濃縮物的製造方法， 中该微粒的平均粒徑為5〇nm至5〇〇nm。 ⑻上述（3)、（4)、（5)中任—項所述的粉末製造方法 /、中，該微粒的平均粒徑為5〇nm至5〇〇]加。 (9)在上述⑴所述的高濃度微粒濃縮物中，含有低濃 3】6920 .200538404 度微粒的溶液為C Μ P廢水。 (1 0)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（1)或（6)所述的高濃度微粒濃縮物中，該 微粒至少含有S i〇2。 (12)在上述（2)或（7)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)在上述（3)、（4)、（5)中任一項所述的粉末製造方 春法中，該微粒至少含有Si〇2。 由、上t Si〇2疋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（1)所述的高濃度微粒濃縮物中，含有低濃 度Μ粒的溶液係經由酸性C μ p蘇p #上人a η 幻王廢水和鹼性cmp廢水混 合，並調至ρΗ3至8而成。 ' ()在上述⑺所述的南濃度微粒濃縮物的製造方法 二7广，的落液係經由酸性cmp廢水和驗性 CMP廢水〜合，亚將pH調整至3至8而成。 粒至^二1〇述⑴'或：斤述的高濃 寸主/ 3有s】o2、氧化鈽、氧化鋁、二 化物、氧化物冬I氯氧化鐵二^ ^ t (s} Γ34 ^ ^ ^ ^ ^ ^ t ϋ 饵芏乂 3有Sl〇2、氧化鈽、氧化叙、一片 金屬氫氧化物、氧化物、陶莞、 -乳化鈦、 0…述(3)、(4)、(5)中任一：：=或氟化句。 員所述的粉末製造方 3l6Q?n 9 •200538404 :中，上述微粒至少含有叫、氧化鈽、氧化紹、二氧化 =金屬氫氧化物、氧化物 '料、銦、氫氧化鐵或氟化 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)所述的粉末製造方法中，上述微粒至少 s有、氧化鈽、氧化紹或二氧化欽。 姑例如，可將下述⑽廢水中所含的上述Sl〇2、氧化 飾、氧化I呂、二氧化鈦製成用途廣泛、附加價值高的粉末。 ⑽在上述（3)、（4)、（5)、⑻、（13)、（18)、 : 員所述的粉末製造方法，，所得到的粉末比 l〇nr/g 至 400 m2/g。 马 經由乾燥，可使所得粉末比表面積增大。進而， 變更乾燥條件，可將所得粉末比表面積控制在合適的Γ度 (21) -種粉末’其特徵在於由上述(5)、⑻ 、 =9) (20)中任—項所述㈣末製造方法得到且該粉末的 均粒徑為5// m至100# m。 (22) -種粉末，係由上述（3)、（4)、（8)、⑴）、（、 (19)、（2G)中任—項所述的粉末製造方法得到。 ,卜二:本發明’可以得到能循環再利用的高濃度漿液及 比4水液附加值高的粉末。 【實施方式] 下面說明本發明的較佳實施方案。 第1圖表示本發明的粉末製造方法中使用的粉 裝置結構。如第1圖所示，本實施方案的粉末製造裳置； 316920 ]0 •200538404 致構成為：處理上述CMP(化學機械研磨）廢水的過濾裝置 1〇;以及將經由該過濾裝置10濃縮至高濃度，例如}重量 、/°至5〇重i %，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 政置10内，如上所述，在孔徑〇 25 # m的過濾膜表面設 置膜組件12’該組件中安裝至少i片或！片以上的形成凝 膠層的凝膠過濾膜。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“Shlrry closer，，（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、二氧化鈦（Ti〇2)粒子等，這些研磨劑微粒是 CMP廢水中的主要成分，另外，還含有作為半導體基板的 SiO2絕緣膜層研磨屑的Si〇2粒子或金屬氫氧化物、氧化 籲物、陶瓷、銦、氫氧化鐵、氟化鈣等。 特別是，半導體基板的Si〇2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]〇〇%是以〇2。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 31 .200538404 這種CMP廢水中微粒的平均粒徑為5〇11111至5〇〇nm， 處於稱作膠體的粒㈣圍，優選5()賊至通常多 數在lOOnm附近。例如，當微粒為以〇2時，呈膠體二氧 化矽狀態。 供給上述過濾裝置1G的含低濃度微粒的溶液，特別是 P笔水的pH。周整至3至8者是優選的。如第2圖所示， 在έ無機4敬粒為1 〇 〇 % S〇从义、曲 /〇 bl〇2的低濃度溶液中，在PH4附近 的比表面積最高，該pH為箄带Because the slurry of Nandodu powder is used for the Makoto Mita, the powder drying time can be shortened, and at the same time, the powder of Nannan can be liquid. (6) The fine particles of the fine particles (6) The high-concentration fine particles according to the above (1) have a concentrated average particle diameter of 50 nm to 500 nm. In the method for producing a high-concentration fine particle concentrate as described in the above item, the average particle diameter of the fine particles is 50 nm to 500 nm. The method for producing a powder according to any one of (3), (4), and (5) above, wherein the average particle diameter of the fine particles is 50 nm to 5000. (9) In the high-concentration particulate concentrate described in the above item (i), the solution containing low-concentration particulates] 6920.200538404 degrees of particulates 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 the above (1) or (6), the fine particles contain at least S 102. (12) In the method for producing a high-concentration fine particle concentrate according to the above (2) or (7), the fine particles contain at least SiO2. (13) In the powder manufacturing method according to any one of (3), (4), and (5), the fine particles contain at least Si02. Since tSi02 is used as a useful substance in reagents in a wide range of fields, it can be added to a powder to obtain increased added value. (14) In the high-concentration microparticle concentrate described in (1) above, the solution containing low-concentration M particles is mixed via acidic C μ p Sup # 上人 a η Phantom wastewater and alkaline cmp wastewater, and adjusted To ρΗ3 to 8. '() The method for producing a nano-concentration microparticle concentrate as described in (2) above. The liquid falling system is made by adjusting the pH of the acidic wastewater and the CMP wastewater to 3 to 8. Grain to ^ 2 10 ⑴ ⑴ 或 or: 述 主 high-concentration inch master / 3 s] o2, hafnium oxide, alumina, dioxide, oxide winter I iron oxychloride ^ ^ t (s) Γ34 ^ ^ ^ ^ ^ ^ t ϋ bait 3 is S102, osmium oxide, oxidizing oxide, a piece of metal hydroxide, oxide, ceramic,-emulsified titanium, 0 ... (3), (4), ( 5) Any one of: == or fluorinated sentence. The powder manufacturer described in the member 3116Q? N 9 • 200538404: In the above-mentioned particles, at least, the particles contain at least, osmium oxide, oxide, oxide = metal hydroxide, oxidation. The particles, indium, ferric hydroxide, or fluorinated particles are all useful metal compounds, and it is desirable to recycle them. (19) In the method for producing a powder according to (5) above, the particles have at least s and rhenium oxide. For example, the above-mentioned S102, oxidation ornament, oxidation oxide, and titanium dioxide contained in the following 二 wastewater can be made into a powder with a wide range of uses and high added value. ⑽In the above (3 ), (4), (5), osmium, (13), (18), and the powder manufacturing method described above, the obtained powder ratio is 10nr / g to 400 m2 / g. By drying, the specific surface area of the obtained powder can be increased. Furthermore, by changing the drying conditions, the specific surface area of the obtained powder can be controlled to an appropriate Γ degree (21)-a kind of powder ', which is characterized by the above (5), ⑻, = 9 ) Obtained in any one of the items (20), obtained by the method for making crumbs and the average particle diameter of the powder is 5 // m to 100 # m. (22) A powder obtained by the powder manufacturing method described in any one of (3), (4), (8), (ii), (, (19), (2G) above., Bu II: According to the present invention, a high-concentration slurry that can be recycled and a powder with a higher added value than 4 aqueous liquids can be obtained. [Embodiment] The preferred embodiment of the present invention will be described below. Fig. 1 shows the use in the powder manufacturing method of the present invention. The structure of the powder device. As shown in FIG. 1, the powder manufacturing apparatus of the present embodiment; 316920] 200538404 so as to constitute: a filter device 10 for treating the above-mentioned CMP (chemical mechanical polishing) wastewater; and will pass through the filter The apparatus 10 is concentrated to a high concentration, for example, a vacuum freeze drier 20 for vacuum-drying the slurry-liquid in a slurry-liquid under vacuum freeze-drying, preferably} by weight, / ° to 50% by weight, preferably (at 20% by weight to 50% by weight). In the filtration unit 10, as described above, a membrane module 12 'is provided on the surface of the filter membrane having a pore size of 0.25 mm, and at least one or more gel filtration membranes forming a gel layer are installed in the module. In addition, the pump 14 is used to suck wastewater from the gel filtration membrane of the membrane module 12 The filtering device 10 is preferably, for example, "Shlrry closer," (trade name) (manufactured by Sanyo Water Technology Co., Ltd.) which generates and generates only slight bubbles on the membrane surface. As the fine particles in the CMP wastewater, for example, Examples of abrasives used in CMP systems include cerium oxide (CeO2), silica particles, alumina particles, and titanium dioxide (Ti02) particles. These abrasive particles are the main component of CMP wastewater. It also contains SiO2 particles or metal hydroxides, oxides, ceramics, indium, iron hydroxide, calcium fluoride, etc., which are abrasive particles of SiO2 insulating film layers of semiconductor substrates. In particular, SiO2 of semiconductor substrates Insulating film layer, CMP wastewater generated during polishing with an abrasive composed of silicon dioxide particles. Because its pH is close to 10, it is called alkaline CMP wastewater. The alkaline cMp wastewater is inorganic particles in CMP wastewater Almost] 〇〇% is 〇2. Moreover: As CMP wastewater, the above-mentioned alkaline CMP wastewater accounts for a large proportion. On the other hand, it is generated during polishing in the semiconductor field or other fields, and contains The CMP wastewater of many metals other than SiO2 is called acidic CMP wastewater because it is close to 2. 316920 31 .200538404 The average particle size of particles in this CMP wastewater is 5011111 to 500nm, which is between The size of the granules called colloids is preferably 5 () to usually around 100 nm. For example, when the particles are θ2, it is in the state of colloidal silica. The solution containing the low-concentration particles supplied to the filter device 1G, In particular, the pH of P pen water. It is preferable to round to 3 to 8. As shown in Fig. 2, the granules in the inorganic powder are 100% S〇 from Yi, Qu / 〇bl〇2 as low as In the concentration solution, the specific surface area is highest near PH4, which is the pH band
细、 P馮寺毛點。另外，採用上述粉末 衣造裝置進行濃縮·直空A# π ^ 7凍乾燥後的Si02的粉末比表面 積’為作為高效能粒子可佶用 」便用的比表面積為130m2/g或 130m2/g以上，希望η在δ戎s以π ^ 士 、曲& _ 牡S忒8以下。另一方面，當含低 /辰度Μ粒的溶液pH小於3日李 μ 、$比表面積不僅减少，而且， 在過濾、裝置1 0中進行灑辕考 理邦。 辰鈿處理蚪有時會發生腐蝕，因而不 另外，對於含低濃度微粒_ 滚乾燥後的粉末比表面積的心 辰难具工冷 度溶液為例，用第3圖至第=以僅含§_ u王弟5圖加以詳細說明。 如弟3圖所示，合^ Μ 2 4粒的溶液pH比等電f纟p 低，即低於4時（在這裡稱作 寻电.，占ΡΗ4 的帶電粒子㈣斥力的作用 ^ ㈣㈣表面 以凝聚，比表面積有變二:=離㈣，結㈣ 當含3102微粒的溶液ρΗ二 如弟4圖所不， 這裡稱作“驗性溶液，，），妳由微;^ ΡΗ4大，即大於4時（在 的作用，粒子間距離拉;面的帶電粗子間排斥力 夺開、结果是難以凝聚，比表面積有 316920 .200538404 變小的傾向。另外，如筮ς囬"_ , 1如乐5圖所不，當含Si〇2微粒的溶液 PH為等電點pH 4時（在這裏稱作“中性溶液，,），由於微粒 表面不帶電，粒子間不發生排斥作用，粒子間距離接近， 粒子易於凝聚，結杲是比表面積加大。 作為上述含低濃度微粒的溶液pH調整方法，可以舉 ::⑷把^上述酸性CMP廢水和驗性⑽廢水加以適當二 口可以5周整至pH3至8。⑻向酸性及/或驗性CMp廢水 中"』、、= pH 5周即劑’可以配製經過pH調節後的含低濃度微 津的/合液。在這裏，作為pH調節劑，例如可以採用氫氧 化鉀、氫氧化銨等。作為其他方案，⑷向上述過濾裝置ι〇 中七、未5周節pH的含低濃度微粒的溶液後，可以用上述 PH調節劑適當調節上述過濾裝置1〇中的pH。另外，作為 另一實施方案，⑷把含有未調整過pH的低濃度微粒溶液 供給上述過濾裝置10,在該過濾裝置1〇内邊監測pH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 籲高濃度微粒的漿液。 、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 ~凍乾燥而成者。在這種情况下，由於可以得到純度高的 純S]〇2粉末，故可再用作高附加值粉末。 曲另外，用上述過濾裝置10將上述含低濃度微粒的溶液 展縮至南濃度，以i重量％至50重量％為較佳，以濃縮至 2〇重1%至50重量％的漿液為更佳。特別是將濃縮至 重量％至50重量％的高濃度的漿液進行真空冷凍乾燥，可 316920 .200538404 以大幅縮短乾燥時間，另 在本實施方案中末的粒徑。 -的乾燥器，優選採用直含高濃度微粒的漿液 * 餘的條件，可根據含高濃产 乍為真工々凍乾 如在鐵至(TC，以6(rr 水液濃度適當選擇，例 (冰溫财佳，真空mrc為較佳、以俄至-c 為較佳。作為真空冷凍：：g(2·7至6.7hpa(N/-2)) “TFD-55〇-8sP，,（寶酒公司製）“ ☆，例如，可以採用 按照本發明人的實驗，採用 3〇重量％的襞液中的微粒平均粒徑為18，^置士 1〇〉辰縮至 行粉碎，其粉末的 結體故用研銶進行粉碎。該粉碎過乾白^末由於微粒變成燒 燥為較佳。叫要仔到粒徑小的粉末時，以實施冷康乾 為經由上述過濾裝置1〇 曲 高濃度毁液，既可以直接使用，也可 ==濃縮物的 化妝材料、研磨劑。另外，可柜 梵的瓷釉、 的濃縮物中添加適當的其他添加劑。 述高濃度微粒 採用上述粉末製造裝置， 乾燥得到的粉末平均粒徑為 M T進行真空冷凍 末為斤 為^至100^，例如，者扒 刀為s】o2 ¥，可以得到平均粒經約 田未刀 解二氧化矽（fumed si]ica)。 末，即熱 另外，把根據上述過遽農置】0得到的含高壤度微粒榮 3)6920 14 200538404 液，乾燥後再根據所得到的粉末粒經，在再分散時調 粒漿液濃度後進行乾燥是優選的。 正Λ 在上述乾燥步驟中，例如在真空冷凍乾燥步驟钚 由適當調整真空狀態及乾燥溫度，可以 二 徑。因此，根據所得到的粉末用途，把所希望 加以精製。 的才刀末 得到的粉末比表面積為1〇m2/g至4〇叫 =行上述乾燥，可以使所得到的粉末比 大進一步，經由改變乾燥條件，可把所得到、 面積控制在合適的程度。 -末比表 例如％土::ί製造裝置及粉末製造方法得到的粉末， :士適合做為多孔材料、化妝材料、吸附 =、親水處理劑、分析儀器用填料(例如，氣 寻填枓）、印刷用調色劑的添加劑等。 色。曰法 高濃度漿液，可根據該漿 ►用途’例如，可用作陶究器的究二選Γ 在CMP廢水進行乾燥得到的粉末可以再 舍^。 適當的領域，例如客 再利用於任何 過濾助劑、親水成制、丄化，材料、吸附劑、陶兗、 法等填料）、印刷义用二:析儀器用填料（例如，氣體色譜 【圖式簡單說明】 添加劑等均適用。 圖。弟]圖係說明本發明實施方案的粉末製造裝置之構造 的 第2圖係含低濃度S]02微粒之溶液之邱和所得到 316920 35 200538404Fine, P Feng Temple hair spots. In addition, using the above powder coating device for concentration and direct air A # π ^ 7 The specific surface area of SiO2 powder after freeze-drying is 'available as high-performance particles.' The specific surface area for use is 130m2 / g or more than 130m2 / g It is hoped that η is below δ Rong s with π ^ 、, qu & S 忒 8. On the other hand, when the pH of the solution containing low / C degree M particles is less than 3 days, the specific surface area is not only reduced, but also filtered and filtered in the device 10. Cinnamon treatment may cause corrosion, so it is not necessary to use a solution containing low concentration of fine particles _ tumble dried powder specific surface area, which is difficult to produce a cooling solution, for example. _ u brother 5 picture for details. As shown in Figure 3, the pH of the solution of He 2 M 2 4 particles is lower than the isoelectric f 纟 p, that is, less than 4 (herein referred to as electricity seeking.), Which accounts for the repulsive force of charged particles of PΗ4 ^ ㈣㈣ surface With agglomeration, the specific surface area is changed as follows: = Li, ㈣ When the solution containing 3102 particles ρΗ is not as shown in Figure 4, here is called "experimental solution,"), you are fine; ^ ΡΗ4 large, ie When it is greater than 4, the repulsive force between charged particles is pulled away from the surface, the result is that it is difficult to condense, and the specific surface area tends to be smaller 316920 .200538404. In addition, such as 筮 ς 回 " _, 1 As shown in Figure 5, when the pH of the solution containing SiO2 particles is the isoelectric point pH 4 (herein referred to as "neutral solution,"), since the surface of the particles is not charged, repulsion does not occur between the particles. The distance between the particles is close, the particles are easy to aggregate, and the specific surface area is increased. As a method for adjusting the pH of the solution containing low-concentration particles, the following methods can be used: 5 weeks to pH 3 to 8. ⑻In acidic and / or empirical CMP wastewater " 』,, = pH 5 The instant agent can be prepared with a low concentration of microjin / mix solution after pH adjustment. Here, as the pH adjusting agent, for example, potassium hydroxide, ammonium hydroxide, etc. can be used. 〇 After the solution containing low-concentration particles at a pH of less than 5 weeks, the pH in the filtering device 1 can be appropriately adjusted by using the above-mentioned pH adjuster. In addition, as another embodiment, The low-concentration particulate solution is supplied to the above-mentioned filtering device 10, and the concentration treatment is terminated when the pH exceeds the range of 3 to 8 while monitoring the pH in the filtering device 10, which can be used as a slurry containing high-concentration particulates. In the embodiment, the CMP wastewater is particularly preferably obtained by adjusting the pH of the alkaline CMP wastewater mainly composed of SiO 2 particles and performing concentration, vacuum, and freeze drying. In this case, high purity can be obtained. Pure S] 〇2 powder, so it can be reused as a high-value-added powder. In addition, the above-mentioned filter device 10 is used to stretch the solution containing low-concentration particles to the south concentration, with i% to 50% by weight as a comparison. Good It is more preferable to reduce the slurry to 20% by weight to 1% to 50% by weight. Especially, the high concentration slurry concentrated to 50% by weight to 50% by weight is subjected to vacuum freeze-drying, which can be 316920.200538404 to greatly reduce the drying time. The particle size in this embodiment.-The desiccator preferably uses a slurry containing high-concentration particles. The remaining conditions can be lyophilized, such as in iron to (TC, 6 (rr water liquid concentration is appropriately selected, for example (ice temperature is good, vacuum mrc is better, Russia to -c is better. As vacuum freezing: g (2 · 7 to 6.7hpa (N / -2)) "TFD-55〇-8sP," (manufactured by Takara Shuzo Co., Ltd.) ☆ For example, according to the inventor's experiment, the average particle diameter of 30% by weight of the mash solution is 18, and the ratio is 1 〇> Chen was shrunk to a line for pulverization, and the structure of the powder was pulverized by using a mill. The pulverized overdried white powder is preferable because the particles become dried. When the powder is called a powder with a small particle size, a cold Kanggan solution is used to pass through the above-mentioned filtering device, and it can be used directly, or it can be used as a cosmetic material or abrasive concentrate. In addition, appropriate other additives are added to the enamel and concentrate of the cabinet. The above-mentioned high-concentration particles use the above-mentioned powder manufacturing device, and the average particle diameter of the powder obtained by drying is MT and the vacuum freezing is ^ to 100 ^, for example, the chopping knife is s] o2 ¥, and the average particle size can be obtained by Fumed si] ica. Finally, it is hot. In addition, the highly soil-containing microparticles obtained according to the above-mentioned farms] 0) 3,6920 14 200538404 liquid, after drying, then according to the obtained powder particles, adjust the slurry concentration during redispersion. Drying is preferred. In the above drying step, for example, in the vacuum freeze-drying step, the diameter can be changed by appropriately adjusting the vacuum state and the drying temperature. Therefore, the desired powder is used to refine it. The specific surface area of the powder obtained at the end of the knife is 10m2 / g to 40. The above drying can make the obtained powder ratio larger. By changing the drying conditions, the obtained area can be controlled to an appropriate level. . -The final ratio table, for example, the powder obtained by the manufacturing equipment and powder manufacturing method, is suitable for porous materials, cosmetic materials, adsorption =, hydrophilic treatment agents, and fillers for analytical instruments (for example, gas seeking filling) , Additives for printing toners, etc. color. Said method A high-concentration slurry can be used according to the slurry ►Applications “For example, it can be used as a researcher of a ceramic pottery. The powder obtained by drying in CMP wastewater can be used again. Appropriate fields, such as customer reuse in any filter aid, hydrophilic preparation, chemical conversion, materials, adsorbents, pottery, method and other fillers), printing purposes 2: analytical instrument fillers (for example, gas chromatography [Figure Simple description of the formula] Additives are applicable. Figure. Brother] Figure 2 illustrates the structure of the powder manufacturing device according to the embodiment of the present invention. Figure 2 shows the solution obtained by Qiu He from a solution containing low concentration S] 02 particles. 316920 35 200538404
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微粒之溶液中以〇 微粒的表面狀態之模式圖。 “第4圖係鹼性、含有低濃度Si〇2微粒之溶液 微粒的表面狀態之模式圖。 2 第5圖係Si〇2等電點附近的含 溶液中3丨02微粒的表面狀能 ，低〉辰度义〇2微粒之 【主要元件符號說明】 之核式圖。Relationship between specific surface area of SiO2 powder. Fig. 3 is a schematic diagram showing the surface state of 0 particles in an acidic, low-concentration SiO 2 particle solution. "Figure 4 is a schematic diagram of the surface state of a solution particle that is alkaline and contains low concentration of SiO2 particles. 2 Figure 5 is the surface energy of 3 丨 02 particles in a solution near the isoelectric point of SiO2, Low> Chen Duyi 0 2 particle [nuclear component symbol] nuclear diagram.
10 14 20 12 16 膜組件 傳送泵 過濾裝置 栗 真空冷凍乾燥裝置10 14 20 12 16 Membrane module Transfer pump Filtration pump Chestnut Vacuum freeze dryer
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