TWI759787B - Method for processing waste polishing solution and waste solution containing hydrofluoric acid - Google Patents
Method for processing waste polishing solution and waste solution containing hydrofluoric acid Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C01B33/00—Silicon; Compounds thereof
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Abstract
Description
本揭露是有關於一種研磨廢液與含氫氟酸廢液的處理方法，且特別是有關於一種能夠分離出金屬氟化物與氟矽酸鹽的對於研磨廢液與含氫氟酸廢液的回收方法。The present disclosure relates to a method for treating grinding waste liquid and hydrofluoric acid-containing waste liquid, and in particular, to a method for treating grinding waste liquid and hydrofluoric acid-containing waste liquid that can separate metal fluorides and fluorosilicates. recycling method.
在半導體產業、面板產業、光伏產業等科技產業的製程中，需大量使用包含蝕刻液與研磨液的化學溶液。此些化學溶液經使用過後成為廢液。不僅廢液中的毒性物質可能對環境造成影響，且廢液中仍可能含有一些具有經濟價值的成分。隨著科技產業的進展，廢液的產量也日益提高。因此，用於降低廢液的毒性與分離出廢液中具有經濟價值的成分的方法逐漸成為本領域中重要的課題之一。In the manufacturing process of the semiconductor industry, panel industry, photovoltaic industry and other technological industries, a large amount of chemical solutions including etching solution and polishing solution are used. These chemical solutions become waste liquids after use. Not only the toxic substances in the waste liquid may have an impact on the environment, but also the waste liquid may still contain some economically valuable components. With the development of the technology industry, the output of waste liquid is also increasing. Therefore, a method for reducing the toxicity of the waste liquid and separating the economically valuable components in the waste liquid has gradually become one of the important issues in the field.
本揭露提供一種用於處理研磨廢液與含氫氟酸廢液的方法，能夠降低上述廢液的毒性且分離出廢液中具有經濟價值的回收產物。The present disclosure provides a method for treating grinding waste liquid and hydrofluoric acid-containing waste liquid, which can reduce the toxicity of the above-mentioned waste liquids and separate the recovered products with economic value from the waste liquids.
本揭露的研磨肥液與含氫氟酸廢液的處理方法，包括：提供研磨廢液，其中所述研磨廢液包括能夠與氫氟酸反應生成非水溶性產物的氧化物；提供另一廢液，其中所述廢液含有氟矽酸與所述氫氟酸；混合所述研磨廢液與所述廢液，以形成第一混合液，其中所述研磨廢液中的所述氧化物與所述廢液中的所述氫氟酸反應而形成非水溶性的氟化物；對所述第一混合液進行第一過濾；取出所述第一混合液的包括所述氟化物的第一回收產物；提供能夠與所述氟矽酸反應而生成氟矽酸鹽的金屬鹽；混合所述金屬鹽與經取出所述第一回收產物的所述第一混合液，以形成第二混合液，其中所述金屬鹽與所述氟矽酸反應生成非水溶性的所述氟矽酸鹽；對所述第二混合液進行第二過濾；以及取出所述第二混合液的包括所述氟矽酸鹽的第二回收產物。The method for treating grinding fertilizer liquid and hydrofluoric acid-containing waste liquid of the present disclosure includes: providing grinding waste liquid, wherein the grinding waste liquid includes oxides capable of reacting with hydrofluoric acid to generate water-insoluble products; providing another waste liquid liquid, wherein the waste liquid contains fluorosilicic acid and the hydrofluoric acid; mixing the grinding waste liquid and the waste liquid to form a first mixed liquid, wherein the oxide in the grinding waste liquid and the The hydrofluoric acid in the waste liquid reacts to form a water-insoluble fluoride; the first filtration is performed on the first mixed solution; the first recovery including the fluoride is taken out of the first mixed solution product; providing a metal salt capable of reacting with the fluorosilicic acid to generate a fluorosilicate; mixing the metal salt with the first mixed solution from which the first recovered product is taken out to form a second mixed solution, wherein the metal salt reacts with the fluorosilicic acid to form the water-insoluble fluorosilicate; the second mixed solution is subjected to a second filtration; The second recovery product of the acid salt.
在一些實施例中，所述氧化物包括氧化鈰。In some embodiments, the oxide includes ceria.
在一些實施例中，所述氧化物更包括氧化鋁。In some embodiments, the oxide further comprises alumina.
在一些實施例中，所述方法更包括在混合所述研磨廢液與所述廢液之前對所述研磨廢液進行提濃。In some embodiments, the method further includes enriching the grinding waste liquid before mixing the grinding waste liquid with the waste liquid.
在一些實施例中，藉由管式膜提濃法、減壓濃縮法或多效蒸發法對所述研磨廢液進行所述提濃。In some embodiments, the concentration is performed on the grinding waste liquid by a tubular membrane concentration method, a reduced pressure concentration method or a multi-effect evaporation method.
在一些實施例中，含有所述氟矽酸與所述氫氟酸的所述廢液為蝕刻廢液。In some embodiments, the waste liquid containing the fluorosilicic acid and the hydrofluoric acid is an etching waste liquid.
在一些實施例中，所述氟化物包括氟化鈰。In some embodiments, the fluoride comprises cerium fluoride.
在一些實施例中，所述氟化物更包括氟化鋁。In some embodiments, the fluoride further comprises aluminum fluoride.
在一些實施例中，所述金屬鹽包括硫酸鈉，且所述氟矽酸鹽包括氟矽酸鈉。In some embodiments, the metal salt includes sodium sulfate, and the fluorosilicate salt includes sodium fluorosilicate.
在一些實施例中，提供所述金屬鹽的方法包括混合硫酸廢液與含鈉的溶液。In some embodiments, the method of providing the metal salt includes mixing waste sulfuric acid with a sodium-containing solution.
在一些實施例中，所述含鈉的溶液包括氫氧化鈉溶液、氯化鈉溶液、硝酸鈉溶液、磷酸鈉溶液或碳酸鈉溶液。In some embodiments, the sodium-containing solution includes sodium hydroxide solution, sodium chloride solution, sodium nitrate solution, sodium phosphate solution, or sodium carbonate solution.
基於上述，本揭露的對於研磨廢液與含氫氟酸廢液的處理方法包括混合研磨廢液與含氫氟酸廢液，而使研磨廢液中的固態研磨顆粒與氫氟酸反應。如此一來，形成非水溶性的氟化物，且降低混合廢液中的氫氟酸濃度，而降低廢液的毒性。上述氟化物可經取出，而經處理而成為具有經濟價值的回收產物。另一方面，剩餘的廢液可經加入例如是硫酸鹽的金屬鹽，而使廢液中的氟矽酸與此金屬鹽產生反應，以得到非水溶性的氟矽酸鹽。氟矽酸鹽經取出且處理過後可作為另一回收產物。在一些實施例中，上述的金屬鹽可由硫酸、硝酸、磷酸、鹽酸等酸廢液製成。在此些實施例中，上述酸廢液的處理可與研磨廢液及含氫氟酸廢液的處理整合在一起，而可有效地降低對於此些廢液的處理成本。Based on the above, the method for treating the grinding waste liquid and the hydrofluoric acid-containing waste liquid of the present disclosure includes mixing the grinding waste liquid and the hydrofluoric acid-containing waste liquid, so that the solid grinding particles in the grinding waste liquid are reacted with hydrofluoric acid. In this way, a water-insoluble fluoride is formed, the concentration of hydrofluoric acid in the mixed waste liquid is reduced, and the toxicity of the waste liquid is reduced. The above-mentioned fluorides can be taken out and processed to be recovered products with economical value. On the other hand, the remaining waste liquid can be added with a metal salt such as sulfate, and the fluorosilicic acid in the waste liquid can react with the metal salt to obtain a water-insoluble fluorosilicate. The fluorosilicate can be taken out and processed as another recovered product. In some embodiments, the above-mentioned metal salts can be prepared from acid waste liquids such as sulfuric acid, nitric acid, phosphoric acid, and hydrochloric acid. In these embodiments, the above-mentioned treatment of the acid waste liquid can be integrated with the treatment of the polishing waste liquid and the waste liquid containing hydrofluoric acid, so that the treatment cost of these waste liquids can be effectively reduced.
圖1是依照本揭露一些實施例的用於處理研磨廢液與含氫氟酸廢液的方法的流程圖。在一些實施例中，上述方法包括下列步驟。FIG. 1 is a flow chart of a method for treating a polishing waste liquid and a hydrofluoric acid-containing waste liquid according to some embodiments of the present disclosure. In some embodiments, the above method includes the following steps.
請參照圖1，進行步驟S100，以提供研磨廢液。研磨廢液來自於化學機械研磨製程期間經使用的研磨液。舉例而言，此化學機械研磨製程可用於平坦化半導體晶圓上的氧化物（例如是氧化矽）、氮化物（例如是氮化矽）、金屬（例如是鎢、銅）或其組合。然而，上述化學機械研磨製程也可以是用於面板產業、光伏產業等其他產業的化學機械研磨製程，本揭露並不以研磨液所應用的產業為限。研磨液包含研磨顆粒。在外力作用下，研磨顆粒可用於削磨工件的表面。在一些實施例中，研磨顆粒的材料包括氧化矽（例如是二氧化矽）、氧化鋁（例如是三氧化二鋁）以及氧化鈰（例如是二氧化鈰）。此外，研磨液更包括化學藥劑。在一些實施例中，化學藥劑可包括選自由介面活性劑、螯合劑、抑制劑、pH緩衝劑、氧化劑及其類似者所構成的群組中的一或多者。研磨液經使用後其中的研磨顆粒保留下來，且其中的化學藥劑部分地反應後亦保留於研磨廢液中。再者，研磨廢液可能包括自工件移除的材料（例如是含矽材料、銅、鎢等）。Referring to FIG. 1 , step S100 is performed to provide polishing waste liquid. The polishing waste liquid comes from the polishing liquid used during the chemical mechanical polishing process. For example, the CMP process can be used to planarize oxides (eg, silicon oxide), nitrides (eg, silicon nitride), metals (eg, tungsten, copper), or combinations thereof, on semiconductor wafers. However, the above chemical mechanical polishing process can also be a chemical mechanical polishing process used in the panel industry, photovoltaic industry and other industries, and the present disclosure is not limited to the industry to which the polishing liquid is applied. The slurry contains abrasive particles. Under the action of external force, the abrasive particles can be used to grind the surface of the workpiece. In some embodiments, the materials of the abrasive particles include silicon oxide (eg, silicon dioxide), aluminum oxide (eg, aluminum oxide), and cerium oxide (eg, ceria). In addition, the polishing liquid further includes chemicals. In some embodiments, the chemical agent may include one or more selected from the group consisting of surfactants, chelating agents, inhibitors, pH buffering agents, oxidizing agents, and the like. After the grinding liquid is used, the grinding particles in it are retained, and the chemical agent in the grinding liquid is also retained in the grinding waste liquid after being partially reacted. Furthermore, the polishing effluent may include materials removed from the workpiece (eg, silicon-containing materials, copper, tungsten, etc.).
在取得研磨廢液之後，可選擇性地對研磨廢液進行提濃製程。在一些實施例中，可藉由管式膜對研磨廢液進行提濃。在此些實施例中，研磨廢液通過管式膜時，研磨廢液中的小分子物質（例如是水分子）可穿過膜壁而排出管式膜。另一方面，研磨廢液中的大分子物質（例如是研磨顆粒）可通過管式膜的中心通道而被收集，以成為提濃的研磨廢液。在其他實施例中，也可藉由減壓濃縮法、多效蒸發法等方法對研磨廢液進行提濃。After the grinding waste liquid is obtained, the concentration process of the grinding waste liquid can be selectively carried out. In some embodiments, the grinding waste liquid can be concentrated by a tubular membrane. In these embodiments, when the polishing waste liquid passes through the tubular membrane, small molecular substances (eg, water molecules) in the polishing waste liquid can pass through the membrane wall and exit the tubular membrane. On the other hand, macromolecular substances (such as abrasive particles) in the grinding waste liquid can be collected through the central channel of the tubular membrane to become the concentrated grinding waste liquid. In other embodiments, the grinding waste liquid can also be concentrated by a vacuum concentration method, a multi-effect evaporation method, or the like.
在步驟S102中，提供蝕刻廢液。蝕刻廢液來自於蝕刻製程期間經使用的蝕刻液。舉例而言，此蝕刻製程可用於（但不限於）移除半導體晶圓上的材料。在一些實施例中，此蝕刻製程用於移除含矽材料。在此些實施例中，蝕刻液包括氫氟酸。氫氟酸可與含矽材料反應產生水溶性的氟矽酸。此水溶性反應產物與未反應的氫氟酸可存在於蝕刻廢液中。舉例而言，蝕刻廢液的氫氟酸濃度約為10%（以重量百分比計）。In step S102, etching waste liquid is provided. The etching waste liquid comes from the etching liquid used during the etching process. For example, but not limited to, such an etch process can be used to remove material from a semiconductor wafer. In some embodiments, this etch process is used to remove silicon-containing materials. In such embodiments, the etching solution includes hydrofluoric acid. Hydrofluoric acid can react with silicon-containing materials to produce water-soluble fluorosilicic acid. The water-soluble reaction product and unreacted hydrofluoric acid may exist in the etching waste liquid. For example, the concentration of hydrofluoric acid in the etching waste liquid is about 10% (by weight).
在步驟S104中，混合蝕刻廢液與研磨廢液，而形成第一混合液。在有對研磨廢液進行提濃的實施例中，此處所述的研磨廢液為經提濃的研磨廢液。研磨廢液中含有氧化鈰的研磨顆粒與蝕刻廢液中的氫氟酸產生化學反應。在一些實施例中，氧化鈰與氫氟酸的反應如下式（1）所示。 4CeO 2+ 12HF → 4CeF 3+ 6H 2O + O 2（1） 除此之外，在氫氟酸反應物過量的實施例中，研磨顆粒中的氧化鋁可能與氫氟酸產生如式（2）所示的化學反應。 Al 2O 3+6HF →2AlF 3+3H 2O （2） 在此些實施例中，產生包括三氟化鋁的反應產物。另一方面，在氫氟酸反應物並非過量的實施例中，可能不會產生三氟化鋁反應產物。再者，研磨顆粒中的氧化矽可能溶於氫氟酸，而成為水溶性的氟矽酸。氟化鈰（三氟化鈰）與氟化鋁（若有產生）為非水溶性，且可以固態的形式分散於第一混合液中。在一些實施例中，可在室溫（約攝氏15度至約攝氏25度）下混合蝕刻廢液與研磨廢液。此外，可攪拌第一混合液，以使蝕刻廢液與研磨廢液充分反應。 In step S104, the etching waste liquid and the grinding waste liquid are mixed to form a first mixed liquid. In the embodiment in which the grinding waste liquid is concentrated, the grinding waste liquid described here is the concentrated grinding waste liquid. The abrasive particles containing cerium oxide in the polishing waste liquid react chemically with the hydrofluoric acid in the etching waste liquid. In some embodiments, the reaction of ceria with hydrofluoric acid is shown in the following formula (1). 4CeO 2 + 12HF → 4CeF 3 + 6H 2 O + O 2 (1) In addition, in embodiments with excess hydrofluoric acid reactant, the alumina in the abrasive particles may react with hydrofluoric acid to produce the formula (2) ) for the chemical reaction shown. Al 2 O 3 +6HF→2AlF 3 +3H 2 O (2) In these examples, a reaction product comprising aluminum trifluoride is produced. On the other hand, in embodiments where the hydrofluoric acid reactant is not in excess, the aluminum trifluoride reaction product may not be produced. Furthermore, the silicon oxide in the abrasive particles may dissolve in hydrofluoric acid and become water-soluble fluorosilicic acid. Cerium fluoride (cerium trifluoride) and aluminum fluoride (if any) are water-insoluble and can be dispersed in the first mixed liquid in solid form. In some embodiments, the etching waste liquid and the grinding waste liquid may be mixed at room temperature (about 15 degrees Celsius to about 25 degrees Celsius). In addition, the first mixed liquid may be stirred so that the etching waste liquid and the polishing waste liquid are sufficiently reacted.
在步驟S106中，對第一混合液進行第一過濾，以分離第一混合液中的固態物質與液態物質。由上可知，第一混合液中的固態物質可包括氟化鈰（三氟化鈰）、氟化鋁（若有產生），且更可包括未反應的研磨顆粒（包括氧化鋁、氧化鈰及氧化矽）。另一方面，第一混合液中的液態物質可包括氟矽酸水溶液，且可包括研磨廢液中未反應的化學藥劑與未反應的氫氟酸水溶液等。在一些實施例中，藉由離心分離法而將第一混合液的固態物質與液態物質分離。所屬領域中具有通常知識者可依據製程需求而調整離心分離設備的轉速以及離心分離的製程時間，本揭露並不以此為限。在其他實施例中，也可藉由板框過濾法、微孔過濾法、抽氣過濾法、重力沈澱法等方法而過濾第一混合液。In step S106, the first filtration is performed on the first mixed solution to separate solid substances and liquid substances in the first mixed solution. As can be seen from the above, the solid substances in the first mixed solution may include cerium fluoride (cerium trifluoride), aluminum fluoride (if any), and may also include unreacted abrasive particles (including alumina, cerium oxide and silicon oxide). On the other hand, the liquid substance in the first mixed solution may include an aqueous fluorosilicic acid solution, and may include unreacted chemical agents and unreacted hydrofluoric acid aqueous solution in the grinding waste liquid, and the like. In some embodiments, the solid matter and the liquid matter of the first mixed solution are separated by centrifugation. Those with ordinary knowledge in the art can adjust the rotational speed of the centrifugal separation equipment and the process time of the centrifugal separation according to the process requirements, and the present disclosure is not limited thereto. In other embodiments, the first mixed solution can also be filtered by a plate-and-frame filtration method, a microporous filtration method, a suction filtration method, a gravity precipitation method, or the like.
隨後，進行步驟S108，以取出對第一混合液過濾而得到的固態物質，而作為第一回收產物。換言之，第一回收產物可包括氟化鈰（三氟化鈰）、氟化鋁（若有產生），且更可包括未反應的研磨顆粒（包括氧化鋁、氧化鈰及氧化矽）。在一些實施例中，更可藉由例如是水洗的方式將第一回收物表面的水溶性物質去除。如此一來，可進一步純化所取得的第一回收物。隨後，可將第一回收物乾燥，而得到符合銷售規格的氟化鈰（或氟化鈰與氟化鋁）。在一些實施例中，可藉由烘乾機、迴轉乾燥機、瞬間乾燥機（flash dryer）、震動乾燥機等設備來乾燥第一回收產物。在取出第一回收產物之後，剩下的溶液包括氟矽酸水溶液，且可包括研磨廢液中未反應的化學藥劑與未反應的氫氟酸水溶液等。此剩餘溶液在下文中稱為第一過濾溶液。Then, step S108 is performed to take out the solid substance obtained by filtering the first mixed solution as the first recovered product. In other words, the first recovered product may include cerium fluoride (cerium trifluoride), aluminum fluoride (if produced), and more may include unreacted abrasive particles (including alumina, cerium oxide, and silica). In some embodiments, water-soluble substances on the surface of the first recyclate can be removed by, for example, washing with water. In this way, the obtained first recyclate can be further purified. Subsequently, the first recyclate can be dried to obtain cerium fluoride (or cerium fluoride and aluminum fluoride) that meets sales specifications. In some embodiments, the first recovered product may be dried by a dryer, rotary dryer, flash dryer, vibration dryer, or the like. After taking out the first recovered product, the remaining solution includes an aqueous fluorosilicic acid solution, and may include unreacted chemicals and an unreacted aqueous hydrofluoric acid solution in the grinding waste liquid, and the like. This remaining solution is hereinafter referred to as the first filtered solution.
在步驟S110中，提供硫酸鹽溶液。硫酸鹽溶液可以是硫酸溶液經酸鹼中和反應或與金屬鹽溶液反應而得到的硫酸鹽溶液。在一些實施例中，用於上述酸鹼中和的鹼液或金屬鹽溶液包括氫氧化鈉溶液、氯化鈉溶液、硝酸鈉溶液、磷酸鈉溶液、碳酸鈉溶液或其類似者。在此些實施例中，所得的硫酸鹽溶液可包括硫酸鈉溶液。在替代實施例中，也可使用包括其他鹼金屬元素的鹼液或其他金屬鹽類溶液，而得到其他硫酸鹽溶液。舉例而言，在替代實施例中的鹼液可為氫氧化鉀溶液、碳酸鉀溶液等，且所得的硫酸鹽溶液可包括硫酸鉀溶液。在其他實施例中，硫酸鹽溶液也可代換成硝酸鹽溶液、磷酸鹽溶液或金屬氯化物溶液。舉例而言，硝酸鹽可包括硝酸鈉或硝酸鉀；磷酸鹽可包括磷酸鈉或磷酸鉀；且金屬氯化物可包括氯化鈉或氯化鉀。In step S110, a sulfate solution is provided. The sulfate solution can be a sulfate solution obtained by the acid-base neutralization reaction or the reaction with a metal salt solution. In some embodiments, the lye or metal salt solution used for the above acid-base neutralization includes sodium hydroxide solution, sodium chloride solution, sodium nitrate solution, sodium phosphate solution, sodium carbonate solution or the like. In such embodiments, the resulting sulfate solution may include a sodium sulfate solution. In alternative embodiments, lye or other metal salt solutions including other alkali metal elements may also be used to obtain other sulfate solutions. For example, in alternate embodiments the lye may be potassium hydroxide solution, potassium carbonate solution, etc., and the resulting sulfate solution may include potassium sulfate solution. In other embodiments, the sulfate solution can also be replaced by a nitrate solution, a phosphate solution, or a metal chloride solution. For example, nitrates can include sodium nitrate or potassium nitrate; phosphates can include sodium or potassium phosphates; and metal chlorides can include sodium chloride or potassium chloride.
在步驟S112中，混合硫酸鹽溶液與第一過濾溶液。第一過濾溶液中的氟矽酸可與硫酸鹽溶液中的硫酸鹽產生化學反應，而產生氟矽酸鹽與硫酸水。在硫酸鹽溶液包括硫酸鈉的實施例中，氟矽酸與硫酸鹽的反應可如式（3）所示。 H 2SiF 6+ Na 2SO 4→ Na 2SiF 6+ H 2SO 4（3） 在此些實施例中，產生非水溶性的氟矽酸鈉與水溶性的硫酸。在其他實施例中，氟矽酸可與其他種類的硫酸鹽（例如是硫酸鉀）反應，而生成其他種類的氟矽酸鹽（例如是氟矽酸鉀）與硫酸。在下文中，硫酸鹽溶液與第一過濾溶液的混合液稱為第二混合液。在一些實施例中，可在室溫（約攝氏15度至約攝氏25度）下混合硫酸鹽溶液與第一過濾溶液。此外，可攪拌第二混合液，以使硫酸鹽溶液與第一過濾液能夠充分反應。 In step S112, the sulfate solution and the first filtration solution are mixed. The fluorosilicic acid in the first filtration solution can chemically react with the sulfate in the sulfate solution to produce fluorosilicate and sulfuric acid water. In embodiments where the sulfate solution includes sodium sulfate, the reaction of fluorosilicic acid and sulfate may be as shown in formula (3). H 2 SiF 6 + Na 2 SO 4 → Na 2 SiF 6 + H 2 SO 4 (3) In these examples, water-insoluble sodium fluorosilicate and water-soluble sulfuric acid are produced. In other embodiments, fluorosilicic acid may react with other types of sulfates (eg, potassium sulfate) to generate other types of fluorosilicates (eg, potassium fluorosilicate) and sulfuric acid. Hereinafter, the mixed solution of the sulfate solution and the first filtered solution is referred to as the second mixed solution. In some embodiments, the sulfate solution and the first filtered solution can be mixed at room temperature (about 15 degrees Celsius to about 25 degrees Celsius). In addition, the second mixed solution may be stirred so that the sulfate solution and the first filtrate can sufficiently react.
在硫酸鹽溶液被代換成硝酸鹽溶液的實施例中，硝酸鹽可與氟矽酸產生反應，而得到氟矽酸鹽與硝酸。在硫酸鹽水溶液被代換成磷酸鹽水溶液的實施例中，磷酸鹽可與氟矽酸產生反應，而得到氟矽酸鹽與磷酸。另外，在硫酸鹽水溶液被代換成金屬氯化物水溶液的實施例中，金屬氯化物可與氟矽酸產生反應，而得到氟矽酸鹽與鹽酸。In the embodiment in which the sulfate solution is replaced by the nitrate solution, the nitrate can react with fluorosilicic acid to obtain fluorosilicate and nitric acid. In the embodiment in which the aqueous sulfate solution is replaced with an aqueous phosphate solution, the phosphate can react with fluorosilicic acid to obtain fluorosilicate and phosphoric acid. In addition, in the embodiment in which the aqueous sulfate solution is replaced with an aqueous metal chloride solution, the metal chloride can react with fluorosilicic acid to obtain fluorosilicate and hydrochloric acid.
在步驟S114中，對第二混合液進行第二過濾，以分離第二混合液中的固態物質與液態物質。由上可知，第二混合液中的固態物質可包括氟矽酸鹽（例如是氟矽酸鈉）。另一方面，第二混合液中的液態物質可包括硫酸，且可包括未反應的氟矽酸水溶液以及來自於研磨廢液的少量化學藥劑與氫氟酸水溶液等。在下文中，第二混合液中的液態物質可稱作第二過濾溶液。在硫酸鹽被代換成硝酸鹽、磷酸鹽或金屬氯化物的實施例中，第二過濾液中的硫酸可被代換成硝酸、磷酸或鹽酸。在一些實施例中，藉由離心分離法而將第二混合液的固態物質與液態物質分離。所屬領域中具有通常知識者可依據製程需求而調整離心分離設備的轉速以及離心分離的製程時間，本揭露並不以此為限。在其他實施例中，也可藉由板框過濾法、微孔過濾法、抽氣過濾法、重力沈澱法等方法而過濾第二混合液。In step S114, a second filtration is performed on the second mixed solution to separate solid substances and liquid substances in the second mixed solution. As can be seen from the above, the solid substance in the second mixed solution may include fluorosilicate (eg, sodium fluorosilicate). On the other hand, the liquid substances in the second mixed solution may include sulfuric acid, and may include unreacted fluorosilicic acid aqueous solution and a small amount of chemical agent and hydrofluoric acid aqueous solution from the grinding waste liquid. Hereinafter, the liquid substance in the second mixed solution may be referred to as the second filtered solution. In embodiments where sulfate is replaced with nitrate, phosphate, or metal chloride, sulfuric acid in the second filtrate may be replaced with nitric acid, phosphoric acid, or hydrochloric acid. In some embodiments, the solid matter and the liquid matter of the second mixed solution are separated by centrifugation. Those with ordinary knowledge in the art can adjust the rotational speed of the centrifugal separation equipment and the process time of the centrifugal separation according to the process requirements, and the present disclosure is not limited thereto. In other embodiments, the second mixed solution can also be filtered by a plate-and-frame filtration method, a microporous filtration method, a suction filtration method, a gravity precipitation method, or the like.
隨後，進行步驟S116，以取出對第二混合液過濾而得到的固態物質，而作為第二回收產物。換言之，第二回收產物可包括氟矽酸鹽（例如是氟矽酸鈉或氟矽酸鉀）。在一些實施例中，更可藉由例如是水洗的方式將氟矽酸鹽表面的水溶性物質去除。如此一來，可進一步純化所取得的氟矽酸鹽。隨後，可將氟矽酸鹽乾燥，而得到符合銷售規格的氟矽酸鹽。在一些實施例中，可藉由烘乾機、迴轉乾燥機、瞬間乾燥機（flash dryer）、震動乾燥機等設備來乾燥取得的氟矽酸鹽。Then, step S116 is performed to take out the solid substance obtained by filtering the second mixed solution as the second recovered product. In other words, the second recovered product may include a fluorosilicate (eg, sodium fluorosilicate or potassium fluorosilicate). In some embodiments, water-soluble substances on the surface of the fluorosilicate can be removed by, for example, washing with water. In this way, the obtained fluorosilicate can be further purified. The fluorosilicate can then be dried to obtain a fluorosilicate that meets marketing specifications. In some embodiments, the obtained fluorosilicate can be dried by equipment such as dryers, rotary dryers, flash dryers, vibration dryers, and the like.
除此之外，進行步驟S118，而取出第二過濾溶液。由上可知，第二過濾溶液可包括硫酸、硝酸、磷酸或鹽酸，且可能包括未反應的氟矽酸水溶液以及來自於研磨廢液的少量化學藥劑與氫氟酸水溶液等。若所取得的第二過濾溶液包括混合酸，可對第二過濾溶液做進一步中和或其他處理，以達到排放標準。若第二過濾溶液僅包含單一酸（例如是硫酸、硝酸、磷酸或鹽酸），則可回收該單一酸。In addition to this, step S118 is performed, and the second filtration solution is taken out. As can be seen from the above, the second filtration solution may include sulfuric acid, nitric acid, phosphoric acid or hydrochloric acid, and may include unreacted fluorosilicic acid aqueous solution and a small amount of chemicals and hydrofluoric acid aqueous solution from the grinding waste liquid. If the obtained second filtration solution includes mixed acid, the second filtration solution can be further neutralized or otherwise treated to meet the emission standard. If the second filtered solution contains only a single acid (eg, sulfuric, nitric, phosphoric, or hydrochloric acid), the single acid can be recovered.
至此，已完成本揭露一些實施例的對於研磨廢液與含氫氟酸廢液的處理方法。此處理方法包括混合研磨廢液與含氫氟酸廢液，而使研磨廢液中的固態研磨顆粒與氫氟酸反應。如此一來，形成非水溶性的氟化物，且降低混合廢液中的氫氟酸濃度，而降低廢液的毒性。上述氟化物可經取出，而經處理而成為具有經濟價值的回收產物。另一方面，剩餘的廢液可經加入例如是硫酸鹽的金屬鹽，而使廢液中的氟矽酸與此金屬鹽產生反應，以得到非水溶性的氟矽酸鹽。氟矽酸鹽經取出且處理過後可作為另一回收產物。在一些實施例中，上述的金屬鹽可由硫酸、硝酸、磷酸、鹽酸等酸廢液製成。在此些實施例中，上述酸廢液的處理可與研磨廢液及含氫氟酸廢液的處理整合在一起，而可有效地降低對於此些廢液的處理成本。So far, the processing methods for grinding waste liquid and hydrofluoric acid-containing waste liquid according to some embodiments of the present disclosure have been completed. The treatment method includes mixing the waste grinding liquid and the waste liquid containing hydrofluoric acid, so that the solid grinding particles in the waste grinding liquid are reacted with hydrofluoric acid. In this way, a water-insoluble fluoride is formed, the concentration of hydrofluoric acid in the mixed waste liquid is reduced, and the toxicity of the waste liquid is reduced. The above-mentioned fluorides can be taken out and processed to be recovered products with economical value. On the other hand, the remaining waste liquid can be added with a metal salt such as sulfate, and the fluorosilicic acid in the waste liquid can react with the metal salt to obtain a water-insoluble fluorosilicate. The fluorosilicate can be taken out and processed as another recovered product. In some embodiments, the above-mentioned metal salts can be prepared from acid waste liquids such as sulfuric acid, nitric acid, phosphoric acid, and hydrochloric acid. In these embodiments, the above-mentioned treatment of the acid waste liquid can be integrated with the treatment of the polishing waste liquid and the waste liquid containing hydrofluoric acid, so that the treatment cost of these waste liquids can be effectively reduced.
S100、S102、S104、S106、S108、S110、S112、S114、S116、S118:步驟S100, S102, S104, S106, S108, S110, S112, S114, S116, S118: Steps
圖1是依照本揭露一些實施例的用於處理研磨廢液與含氫氟酸廢液的方法的流程圖。FIG. 1 is a flow chart of a method for treating a polishing waste liquid and a hydrofluoric acid-containing waste liquid according to some embodiments of the present disclosure.
S100、S102、S104、S106、S108、S110、S112、S114、S116、S118:步驟S100, S102, S104, S106, S108, S110, S112, S114, S116, S118: Steps
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| TWI231805B (en) * | 2002-06-07 | 2005-05-01 | Showa Denko Kk | Process for recovering rare earth oxide from waste liquid containing rare earth elements, and process for producing rare earth oxides by the recovering process |
| TW200745317A (en) * | 2006-04-07 | 2007-12-16 | Seimi Chem Kk | Method for regenerating cerium-based abrasive |
| TWI499481B (en) * | 2010-02-15 | 2015-09-11 | Mitsui Mining & Smelting Co | Recycle method of ceric abrasive |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202202452A (en) | 2022-01-16 |
| CN113912014A (en) | 2022-01-11 |
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