12973528 〇twfl.doc/d 97-04-03 九、發明說明： 【發明所屬之技術領域】 本發明是有關於-種去除溶液 漆液處理方法，且特別是有關於—種去除石的方，與 矽的方法與廢水處理方法。 中之二氧化 【先前技術】 '於全世 在半導體製程巾，化學機械研 界的晶圓薇，可以說是一個非常重 磨廢水的組成十分複雜，水中的懸浮固體物含量 一 般對化學機械研磨廢水的處理分為二種， 化學混凝的方式將化學機械研磨廢水進行處理不==用 另種方式係使用過渡機制來進行回收處理。 由於化學機械研磨廢水中，粒狀物及二氧化石夕的含量 相當，，使得在+進行過濾機制時，過濾膜管非常容易堵塞， 使膜官的使用壽命減低。一般在膜管堵塞嚴重時，係進行 鹼洗來，除堵塞，其係利用二氧化矽在高pH值的環境中， 具有較咼溶解度的特性。然而，二氧化石夕在值大於12 的環境中，僅能溶解1000ppm左右，且需要經過一段長時 間的停留及攪拌，效果有限，無法解決膜管堵塞的問題。 此外，以驗洗清除堵塞物體的方式，只是單純的利用 簡單的物理方法，在清洗的過程中，並沒有任何的化學反 應發生，所以清洗速度較慢。而且，因為清洗效果不佳， 使得膜管在使用二年半左右，即發生堵塞無法使用，需進 行更換，所耗費的人力與金錢成本則相當可觀。 5 1297328 15510twfl.d〇c/d 97-04 一 〇3 【發明内容】 石夕 的方ΐ發:Γ目的就是在提供一種去除廢液中之二氧細 =廢 化與的另—目的是提供—種廢水處理方法，係利用 堵;氧峨變成氣態物質’以達到去除膜管中 人本發明提出一種去除廢液中之二氧化石夕的方法，係將 二有二^的廢液，於—溫度下加人含有氟離子的溶 液，與廢液混合產生化學反應而生成一生成物。 依照本發明的較佳實施例所述之去除廢液中之二氧化 ft方ίη’上述之含有氟離子之溶液的氣離子濃度例如在 lwt% 〜4〇wt%之間。 依照本發明的較佳實施例所述之去除廢液中之二氧化 !=容i述之含有氣離子的溶液例如為氣化録溶液或 依照本發明的較佳實施例所述之去除廢液中之二氧化 石夕的方法，上述之生成物例如為氣態化合物。 氧化 依照本發明的較佳實施例所述之去除廢液中之 矽的方法，上述之氣態化合物例如為四氟化矽。 依照本發明的較佳實施例所述之去除廢液中之二氧化 矽的方法，上述之溫度例如在1(rc〜5〇〇c之間。 本發明另提出一種廢水處理方法，係針對-膜管所進 行。此膜管t存在有含第一溶液與含有二氧化矽之第二溶 6 1297328 15510twfl.doc/d 97-04-03 液的廢水。首先，進行第一清洗步驟，以將膜管中的第一 溶液之濃度降至第一濃度。接著，將含有氟離子之第三溶 液於一溫度下通入膜管中，與第二溶液產生化學反應而生 成一生成物。之後，進行第二清洗步驟，將未反應的第三 溶液之濃度降至第二濃度。 依照本發明的較佳實施例所述之廢水處理方法，上述 之第一溶液中例如含有可與含氟離子之溶液產生放熱反應 的物質。 依照本發明的較佳實施例所述之廢水處理方法，上述 之弟一溶液包括雙氧水。 依照本發明的較佳實施例所述之廢水處理方法，上述 之第一清洗步驟包括利用清水沖洗(flush)膜管。 依A?、本發明的較佳實施例所述之廢水處理方法，更可 =在第一清洗步驟之後，進行檢測步驟，以檢測殘留之該 第一溶液之濃度。 μ 依R?、本發明的較佳實施例所述之廢水處理方法，上述 之檢測步驟包括利用雙氧水試紙測量殘留的第一溶液之濃 度。 ⑤ 依照本發明的較佳實施例所述之廢水處理方法，上述 之弟一濃度例如為小於ΙΟρρΠΙ。 依A?、本發明的較佳實施例所述之廢水處理方法，上述 之第三溶液的氟離子濃度例如在lwt%〜4〇wt%之間。 依R?、本發明的較佳實施例所述之廢水處理方法，上述 之第三溶液為氟化銨溶液或氟化氫銨溶液。 7 1297328 15510twfl.doc/d 97-04-03 依知、本發明的較佳實施例所述之廢水處理方， 之溫度在10°C〜50°C之間。 处 依照本發明的較佳實施例所述之廢水處理方法，12973528 〇twfl.doc/d 97-04-03 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for treating a solution varnish, and in particular to a method for removing stone, Method with hydrazine and wastewater treatment methods. Dioxide in the prior art [Prior technology] 'The whole world in the semiconductor process towel, the chemical vapor research circle of wafers, can be said that the composition of a very heavy grinding wastewater is very complicated, the suspended solid content in water is generally chemical mechanical grinding The treatment of wastewater is divided into two types. The chemical coagulation method treats the chemical mechanical grinding wastewater. == Another way is to use a transition mechanism for recycling. Since the content of the granular material and the dioxide dioxide in the chemical mechanical polishing wastewater is equivalent, the filtration membrane tube is very likely to be clogged when the filtration mechanism is performed, and the service life of the membrane official is reduced. Generally, when the membrane tube is clogged, the alkali is washed, and in addition to clogging, it utilizes cerium oxide in a high pH environment and has a relatively high solubility characteristic. However, in an environment where the value is greater than 12, the dioxide can dissolve only about 1000 ppm, and it takes a long period of time to stay and stir, and the effect is limited, and the problem of clogging of the membrane tube cannot be solved. In addition, in the manner of cleaning and clogging objects, the simple physical method is used, and no chemical reaction occurs during the cleaning process, so the cleaning speed is slow. Moreover, because the cleaning effect is not good, the membrane tube is used for about two and a half years, that is, the blockage cannot be used, and it needs to be replaced, and the labor and money costs are considerable. 5 1297328 15510twfl.d〇c/d 97-04 一〇3 [Summary of the Invention] Shi Xi’s Fang Weifa: The purpose of the project is to provide a kind of dioxin removal in the waste liquid. - a method for treating wastewater, using plugging; oxo becomes gaseous substance to achieve removal of the membrane tube. The present invention proposes a method for removing the cerium dioxide in the waste liquid, which is a waste liquid of two - Adding a solution containing fluoride ions at a temperature, mixing with the waste liquid to generate a chemical reaction to form a product. The gas ion concentration of the above-mentioned fluoride ion-containing solution in the waste liquid is, for example, between lwt% and 4% by weight, as described in the preferred embodiment of the present invention. The removal of the oxidizing agent in the effluent according to the preferred embodiment of the present invention! The solution containing the ionic ion is, for example, a gasification recording solution or a waste liquid according to a preferred embodiment of the present invention. In the method of arsenic dioxide, the above product is, for example, a gaseous compound. Oxidation A method of removing ruthenium in a waste liquid according to a preferred embodiment of the present invention, such as a ruthenium tetrafluoride. A method for removing cerium oxide in a waste liquid according to a preferred embodiment of the present invention, wherein the temperature is, for example, between 1 (rc and 5 〇〇c). The present invention further provides a wastewater treatment method for The membrane tube is carried out. The membrane tube t has a wastewater containing a first solution and a second solution containing cerium oxide 6 1297328 15510 twfl.doc/d 97-04-03. First, a first washing step is performed to The concentration of the first solution in the membrane tube is reduced to the first concentration. Then, the third solution containing the fluoride ions is introduced into the membrane tube at a temperature to generate a chemical reaction with the second solution to form a product. Performing a second washing step to reduce the concentration of the unreacted third solution to a second concentration. According to the wastewater treatment method of the preferred embodiment of the present invention, the first solution may contain, for example, fluoride-containing ions. The solution produces an exothermic reaction. According to the wastewater treatment method of the preferred embodiment of the present invention, the above-mentioned solution comprises hydrogen peroxide. The wastewater treatment method according to the preferred embodiment of the present invention, the first cleaning described above The step includes flushing the membrane tube with fresh water. According to A?, the wastewater treatment method according to the preferred embodiment of the present invention, further, after the first cleaning step, the detecting step is performed to detect the residual first The concentration of the solution. μ According to R?, the wastewater treatment method of the preferred embodiment of the present invention, wherein the detecting step comprises measuring the concentration of the residual first solution using a hydrogen peroxide test paper. 5 In accordance with a preferred embodiment of the present invention In the wastewater treatment method, the concentration of the above-mentioned brother is, for example, less than ΙΟρρΠΙ. According to A?, the wastewater treatment method according to the preferred embodiment of the present invention, the fluorine concentration of the third solution is, for example, 1 wt% to 4 〇. According to R?, the wastewater treatment method according to the preferred embodiment of the present invention, the third solution is an ammonium fluoride solution or an ammonium hydrogen fluoride solution. 7 1297328 15510twfl.doc/d 97-04-03 The wastewater treatment method according to the preferred embodiment of the present invention has a temperature between 10 ° C and 50 ° C. The wastewater treatment method according to the preferred embodiment of the present invention,
之生成物為氣態化合物。 I 依照本發明的較佳實施例所述之廢水處理方法，上 之氣態化合物為四氟化石夕。 、依照本發明的較佳實施例所述之廢水處理方法，更可 以在產生該生成物後，將生成物通入洗滌塔中。 々依照本發明的較佳實施例所述之廢水處理方法，上述 之弟一清洗步驟為利用清水沖洗(rinse)膜管。 a依照本發明的較佳實施例所述之廢水處理方法，上述 之弟一》辰度例如為小於1 Oppm。 本發明利用二氧化石夕能與含氟物質產生反應的特性， 在廢，=加入氟化銨或氟化氫銨，使其與二氧化矽反應， 產生軋恶的四氟化矽。將本發明應用於化學機械研磨系統 中，可使其廢水回收系統的膜管内的二氧化矽產生反應， 達到去除膜管中堵塞物的目的，以延長膜管使用壽命，節 省更換膜管的人力與設備成本。此外，因本發明係利用化 學反應的方式來去除二氧化矽，而以此方法來進行膜管的 清洗與習知技術中利用驗洗的物理方式比較起來，速度將 更快且效果更佳。 為讓本發明之上述和其他目的、特徵和優點能更明顯 易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說 明如下。 8 J297328 155 lOtwfl .doc/d 97-04-03 【實施方式】 圖1係依照本發賴佳實_之擔絲中之二氧 化石夕的方法所緣示的步驟流程圖。請參照圖i，首先，於 =驟100中’提供一廢液。其中，此廢液中含有二氧化石夕。 在本實施例中，廢液例如為化學機械研磨廢水或封裝測試 廠的研磨廢水。 接著，於步驟102中，將含有氟離子之溶液於一溫度 I’加入廢液中混合產生化學反應而生成一生成物。其中， δ有氟離子之溶液的氟離子濃度例如在lwt%〜4〇wt。乂之 間，其例如為氟化銨溶液或氟化氳銨溶液，而經化學反應 所產生的生成物例如為氣態化合物。在本實施例中，化學 反應的溫度例如在HTC〜5(rc之間，而上述氣態化合物例 如為四氟化矽，而上述之化學反應的反應式式例如為 Si〇4+4HF—^SiF4(g)+2H2〇。 圖2係依照本發明較佳實施例之廢水處理方法所繪示 的步驟流程圖。請參照圖2，首先，於步驟200中，提供 一膜管，在此膜管中存在有含第一溶液與含有二氧化矽之 弟一溶液的廢水。其中，上述廢水例如為化學機械研磨廢 水’膜管例如為微過濾(micro-filter)膜管，且此膜管例如連 接於化學機械研磨裝置，而第一溶液中例如含有可與含氟 離子之溶液產生放熱反應的物質。在本實施例中，第一溶 液例如為雙氧水，其於化學機械研磨廢水中所佔比例例如 為〇·1%〜1%。在另一實施例中，此廢水可以包含有含二 氧化石夕廢液與含金屬廢液，而對於含金屬廢液而言，由於 9 1297328 15510twfl.d〇〇/d 97-04-03 i屬大’為避免堵塞膜管，可以祕含金屬廢液隔 -，再巧_化學混凝的方式進行處理。 Φήίιί著b於步驟搬中，進行第一清洗步驟，以將膜管 、弟一溶液的濃度降至第一濃度。其中，第一清洗步驟 =如為利用清水沖洗膜管，而第—濃度例如為小於 ppm。g為雙氧水與與氣離子接觸時會產生放熱反應， 5免於接下來的步驟巾，因放熱反應造成膜管孔徑變大 或溶=Y故需先用清水將膜管中殘留的雙氧水沖洗乾淨。 在本貝細*例中，更可以在第一清洗步驟之後，進行檢測步 驟，其例如係利用雙氧水試紙測量殘留的第一溶液的濃度。 西然後，於步驟204中，將含有氟離子之第三溶液，於 二溫度下通入膜管中，使之與第二溶液產生化學反應而生 成一生成物。其中，第三溶液的氟離子濃度例如在lwt% 〜40wt%之間，其例如為氟化銨溶液或氟化氫銨溶液，且 溫度例如在1(TC〜5(TC之間。在本實施例中，經化學反應 所產生生成物例如為氣態化合物，其例如為四氟化矽，而 上述之化學反應的反應式式例如為 Si〇4+4HF->SiF4(g)+2H2〇。此外，因為四氟化石夕在大氣中， 遇到水氣會產生氟化氫，其對人體與自然環境會造成危 害，所以更可以在產生生成物後，將生成物通入洗滌塔中， 以避免直接排入大氣中。 之後’為避免當膜管再次通入廢水後，廢水立刻與殘 留的含有氟離子之第三溶液接觸，產生化學反應，所以於 步驟206中，進行第二清洗步驟，將未反應的第三溶液的 !297328 l55l〇twfl.doc/d 97-04-03 第二ΐ度。其中，第二清洗步驟例如為利用清水 冲洗膜官，而第二濃度例如為小於10ppm。 水二卜’ t含有研磨顆粒及氧化劑的化學機械研磨廢 =的處理’在使用膜管過濾廢水之後，則可以_上述本 發明實施财相關步驟來騎_的處理。封裝 測試，的研磨廢水亦可_相_方式進行處理。、 綜上所述，本發明係利用化學反應的方式，使二氧化 石夕產生反雜變錢態㈣。藉減方絲料化賴械 研磨系統巾的膜管，可崎去堵塞在齡_二氧化石夕， 延長膜管㈣壽命，節省更換鮮的人力與設備成本，而 且以此方法來進行膜管的清洗，可加快清洗速度且效果更 佳0 值得注意的是，上述實施賴述之化學機械研磨廢 水，並非侷限於產生自半導體廠中，舉凡具有化學機械^ 磨製程之廠房，例如封裝廠、測試廠等，其所排放出的化 學機械研磨廢水，皆適用於本發明。 此外，因本發明係利用化學反應，將二氧化矽轉變為 氣態物質，所以除了化學機械研磨廢水之外，凡是含有二 氧化矽的溶液，皆可利用本發明來去除其中所含之二氧化 矽，而不只限定於化學機械研磨廢水。 另外，本發明實施例係將廢液中二氧化矽轉變為易於 分離的形式如轉變為易於揮發的氣態物質，然而，本發明 之技術方法亦可應用於含有其他化合物或顆粒的溶液中， 將欲去除的化合物或顆粒經過化學反應，而轉變成氣態物 11 1297織_ 97-04-03 質或其他易於分離的形式。 ^然本發明已以較佳實施纖露如上 何熟習此技藝者，在不脫離本發=: t犯a”田可作些許之更動與潤飾，因此本發明之保罐 •園虽視_之中請專利範圍所界定者鱗。 … 【圖式簡單說明】 圖1係依照本發明較佳實施例之去除廢液中之二5 矽的方法所繪示的步驟流程圖。 〜虱 圖2係依照本發明較佳實施例之廢水處理方法一 的少驟流程圖。 T、、、曰不 【主要元件符號說明】 100〜102、200〜206 :步驟 12The product is a gaseous compound. I In a wastewater treatment method according to a preferred embodiment of the present invention, the gaseous compound is tetrabasic. According to the wastewater treatment method of the preferred embodiment of the present invention, it is further possible to pass the product into the scrubber after the product is produced. According to a wastewater treatment method according to a preferred embodiment of the present invention, the above-described washing step is to rinse the membrane tube with water. A wastewater treatment method according to a preferred embodiment of the present invention, wherein the above-mentioned first degree is, for example, less than 10 ppm. The invention utilizes the characteristics that the dioxide can react with the fluorine-containing substance in the evening, and wastes, = ammonium fluoride or ammonium hydrogen fluoride is added to react with the cerium oxide to produce lanthanum tetrafluoride. The invention is applied to a chemical mechanical polishing system, and the cerium oxide in the membrane tube of the waste water recovery system can be reacted to achieve the purpose of removing the plugging in the membrane tube, thereby prolonging the service life of the membrane tube and saving the manpower for replacing the membrane tube. With equipment costs. Further, since the present invention utilizes a chemical reaction to remove cerium oxide, the cleaning of the membrane tube by this method is faster and more effective than the physical method of using the rinsing in the prior art. The above and other objects, features and advantages of the present invention will become more <RTIgt; 8 J297328 155 lOtwfl .doc/d 97-04-03 [Embodiment] Fig. 1 is a flow chart showing the steps of the method according to the method of the dioxide in the wire of the present invention. Referring to Figure i, first, a waste liquid is supplied at = step 100. Among them, this waste liquid contains sulfur dioxide. In the present embodiment, the waste liquid is, for example, a chemical mechanical grinding wastewater or a grinding wastewater of a packaging test plant. Next, in step 102, a solution containing fluoride ions is added to the waste liquid at a temperature I' to be mixed to generate a chemical reaction to form a product. The concentration of the fluoride ion of the solution having δ fluoride ions is, for example, 1 wt% to 4 〇wt. Between the crucibles, for example, an ammonium fluoride solution or an ammonium cerium fluoride solution, and a product produced by a chemical reaction is, for example, a gaseous compound. In the present embodiment, the temperature of the chemical reaction is, for example, between HTC and 5 (rc, and the gaseous compound is, for example, hafnium tetrafluoride, and the reaction formula of the above chemical reaction is, for example, Si〇4+4HF-^SiF4. (g) +2H2〇 Figure 2 is a flow chart showing the steps of the wastewater treatment method in accordance with a preferred embodiment of the present invention. Referring to Figure 2, first, in step 200, a membrane tube is provided, in which the membrane tube is provided. There is a wastewater containing a first solution and a solution containing cerium oxide. The wastewater is, for example, a chemical mechanical polishing wastewater. The membrane tube is, for example, a micro-filter membrane tube, and the membrane tube is connected, for example. In the chemical mechanical polishing apparatus, the first solution contains, for example, a substance which can generate an exothermic reaction with the fluorine-containing ion solution. In the present embodiment, the first solution is, for example, hydrogen peroxide, and its proportion in the chemical mechanical polishing wastewater is, for example. It is 1%~1%. In another embodiment, the wastewater may contain a waste gas containing cerium dioxide and a metal-containing waste liquid, and for a metal-containing waste liquid, due to 9 1297328 15510 twfl.d〇 〇/d 97-04-03 i is big 'for The clogging membrane tube can be secretly contained in the metal waste liquid compartment, and then processed by chemical coagulation. Φήίιί在b moves in the step, and the first cleaning step is performed to lower the concentration of the membrane tube and the solution To the first concentration, wherein the first cleaning step = if the membrane tube is rinsed with clean water, and the first concentration is, for example, less than ppm. g is hydrogen peroxide and generates an exothermic reaction when in contact with the gas ions, 5 is free from the next step Towels, due to the exothermic reaction, the pore size of the membrane tube becomes larger or dissolves. Y, it is necessary to rinse the residual hydrogen peroxide in the membrane tube with clean water. In this example, the detection step can be performed after the first cleaning step. For example, the concentration of the residual first solution is measured by using a hydrogen peroxide test paper. Then, in step 204, a third solution containing fluoride ions is introduced into the membrane tube at two temperatures to produce a second solution. The chemical reaction produces a product, wherein the third solution has a fluoride ion concentration of, for example, between 1% by weight and 40% by weight, which is, for example, an ammonium fluoride solution or an ammonium hydrogen fluoride solution, and the temperature is, for example, 1 (TC~5 (TC). Between In the present embodiment, the product produced by the chemical reaction is, for example, a gaseous compound such as ruthenium tetrafluoride, and the reaction formula of the above chemical reaction is, for example, Si〇4+4HF->SiF4(g)+2H2 In addition, because tetrafluoride is in the atmosphere, hydrogen fluoride is generated when it encounters moisture, which can cause harm to the human body and the natural environment. Therefore, after the product is produced, the product can be introduced into the washing tower to Avoid direct discharge into the atmosphere. Then, in order to avoid the wastewater being immediately contacted with the residual third solution containing fluoride ions after the membrane tube is re-introduced into the wastewater, a chemical reaction is generated, so in step 206, a second cleaning step is performed. The second reaction of the unreacted third solution was 297328 l55l 〇twfl.doc/d 97-04-03. Among them, the second washing step is, for example, rinsing the film official with fresh water, and the second concentration is, for example, less than 10 ppm. The treatment of the chemical mechanical polishing waste containing abrasive particles and oxidizing agent is carried out after the filtration of the wastewater by the membrane tube, and the treatment of the above-described invention can be carried out. The grinding wastewater from the package test can also be processed in a phase-by-phase manner. In summary, the present invention utilizes a chemical reaction to generate an anti-hybrid state (4). By reducing the membrane tube of the wire-cutting mechanical polishing system towel, the film can be blocked at the age of _ dioxide, the life of the film tube (4) is extended, the replacement of fresh manpower and equipment costs is saved, and the film tube is used in this way. The cleaning can speed up the cleaning and the effect is better. 0 It is worth noting that the above-mentioned chemical mechanical polishing wastewater is not limited to the ones produced in semiconductor factories, such as packaging plants with chemical mechanical grinding processes. The chemical mechanical polishing wastewater discharged by the test plant or the like is suitable for use in the present invention. In addition, since the present invention utilizes a chemical reaction to convert cerium oxide into a gaseous substance, the present invention can be used to remove the cerium oxide contained in the solution containing cerium oxide in addition to the chemical mechanical polishing wastewater. , not limited to chemical mechanical grinding wastewater. In addition, in the embodiment of the present invention, the cerium oxide in the waste liquid is converted into a form which is easy to separate, such as a gaseous substance which is easily volatilized, however, the technical method of the present invention can also be applied to a solution containing other compounds or particles, The compound or particle to be removed undergoes a chemical reaction and is converted into a gaseous form 11 1297 woven or other easily separable form. However, the present invention has been well-received by those skilled in the art, and does not deviate from the present invention: a" can make some changes and retouching, so the cans and gardens of the present invention are regarded as _ BRIEF DESCRIPTION OF THE DRAWINGS The following is a flow chart of the steps of the method for removing two of the waste liquids according to a preferred embodiment of the present invention. A small flow chart of the wastewater treatment method 1 according to the preferred embodiment of the present invention. T, ,, 曰不 [Main component symbol description] 100~102, 200~206: Step 12