TW202035279A - Method for decomposing hydrogen peroxide and device used therein - Google Patents
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Abstract
Description
本發明關於一種過氧化氫的分解方法及使用該方法的裝置，該過氧化氫是廢液中的過氧化氫，該廢液是由半導體的製造步驟等所排出並且含有硫酸和過氧化氫。The present invention relates to a method for decomposing hydrogen peroxide and a device using the method. The hydrogen peroxide is hydrogen peroxide in a waste liquid, which is discharged from semiconductor manufacturing steps and the like and contains sulfuric acid and hydrogen peroxide.
在半導體製程中的晶圓洗淨步驟中，包含硫酸和過氧化氫之SPM(Sulfuric acid Hydrogen Peroxide Mixture，硫酸與過氧化氫之混合液(硫酸雙氧水混合液))被使用來作為洗淨液。該步驟中，在使用SPM後，會對SPM添加過氧化氫來使其氧化力回復，而再度作為洗淨液來利用。然而，在反覆再利用的過程中，源自過氧化氫的水的含量會增加，而降低SPM中的硫酸濃度，從而造成洗淨力衰退，所以需要實行適當的液體交換。在實行該液體交換時所排出的SPM廢液含有過氧化氫，當該過氧化氫超過一定濃度時，就無法作為產業廢棄物來運送(專利文獻1)。 作為將該包含過氧化氫之硫酸廢液中的過氧化氫加以分解並處理的手段，已提案了下述方法：使用大型設備所進行的過氧化氫的熱分解(專利文獻1)；以濃度特別低的過氧化氫為對象並以釩金屬或釩化合物作為觸媒來分解過氧化氫的方法(專利文獻2)等。 [先前技術文獻] (專利文獻)In the wafer cleaning step in the semiconductor process, SPM (Sulfuric acid Hydrogen Peroxide Mixture) containing sulfuric acid and hydrogen peroxide is used as a cleaning solution. In this step, after using SPM, hydrogen peroxide is added to the SPM to restore its oxidizing power, and it is reused as a cleaning solution. However, in the process of repeated reuse, the content of water derived from hydrogen peroxide will increase, and the concentration of sulfuric acid in SPM will be reduced, resulting in a decline in detergency. Therefore, proper liquid exchange is required. The SPM waste liquid discharged during this liquid exchange contains hydrogen peroxide, and when the hydrogen peroxide exceeds a certain concentration, it cannot be transported as industrial waste (Patent Document 1). As a means of decomposing and treating the hydrogen peroxide in the sulfuric acid waste liquid containing hydrogen peroxide, the following method has been proposed: thermal decomposition of hydrogen peroxide using large-scale equipment (Patent Document 1); A method of decomposing hydrogen peroxide using a vanadium metal or a vanadium compound as a catalyst (Patent Document 2) and the like are targeted for particularly low hydrogen peroxide. [Prior Technical Literature] (Patent Document)
專利文獻1：日本特開2013-208602號公報。 專利文獻2：日本特開2002-001358號公報。Patent Document 1: JP 2013-208602 A. Patent Document 2: JP 2002-001358 A.
[發明所欲解決的問題] 然而，本發明人在以硫酸釩作為觸媒來分解硫酸廢液中的過氧化氫時，為了要確認硫酸廢液中的過氧化氫是否已被分解至特定濃度，不得不使用能夠耐硫酸而昂貴的濃度計，故面臨到耗費經費與勞力的問題。 亦即，本發明所欲解決的問題在於經濟且有效地處理包含硫酸和過氧化氫之廢液中的過氧化氫。 [解決問題的技術手段][The problem to be solved by the invention] However, when the inventors used vanadium sulfate as a catalyst to decompose the hydrogen peroxide in the sulfuric acid waste liquid, in order to confirm whether the hydrogen peroxide in the sulfuric acid waste liquid had been decomposed to a specific concentration, they had to use a sulfuric acid resistant product. Expensive densitometer, so it faces the problem of cost and labor. That is, the problem to be solved by the present invention is to economically and effectively treat hydrogen peroxide in a waste liquid containing sulfuric acid and hydrogen peroxide. [Technical means to solve the problem]
為了解決上述問題而努力進行研究的過程中，本發明人發現藉由包含下述步驟之方法，能夠經濟且有效地處理包含硫酸和過氧化氫之廢液中的過氧化氫，並進一步持續研究的結果，從而完成本發明，該等步驟是：將硫酸釩溶液添加在廢液中並進行攪拌的步驟；在廢液到達尖峰溫度(peak temperature)後靜置一定時間的步驟；及，在靜置後進行冷卻的步驟。In the process of diligent research to solve the above problems, the inventor found that the method including the following steps can economically and effectively treat hydrogen peroxide in the waste liquid containing sulfuric acid and hydrogen peroxide, and continue to study As a result, the present invention is completed. The steps are: adding vanadium sulfate solution to the waste liquid and stirring; after the waste liquid reaches the peak temperature (peak temperature), the step is to stand for a certain period of time; and, After setting, perform a cooling step.
亦即，本發明關於以下技術。 [1] 一種過氧化氫的分解方法，該過氧化氫是含有硫酸和過氧化氫之廢液中的過氧化氫；並且，該方法包含以下步驟： 將硫酸釩溶液添加在廢液中並進行攪拌的步驟； 在廢液到達尖峰溫度後靜置一定時間的步驟；及， 在靜置後進行冷卻的步驟。 [2] 如前述[1]所述之方法，其中，廢液是硫酸與過氧化氫之混合液(SPM)的廢液，該硫酸與過氧化氫之混合液被用於半導體的晶圓洗淨。 [3] 如前述[1]或[2]所述之方法，其中，廢液中的過氧化氫為1.6～10.0重量%。That is, the present invention relates to the following technology. [1] A method for decomposing hydrogen peroxide, which is hydrogen peroxide in a waste liquid containing sulfuric acid and hydrogen peroxide; and the method includes the following steps: The step of adding vanadium sulfate solution to the waste liquid and stirring; The step of letting the waste liquid reach its peak temperature for a certain period of time; and, A cooling step is performed after standing. [2] The method described in [1] above, wherein the waste liquid is a waste liquid of a mixed liquid of sulfuric acid and hydrogen peroxide (SPM), and the mixed liquid of sulfuric acid and hydrogen peroxide is used for semiconductor wafer washing net. [3] The method described in [1] or [2] above, wherein the hydrogen peroxide in the waste liquid is 1.6 to 10.0% by weight.
[4] 如前述[1]～[3]中任一項所述之方法，其中，廢液被分配為40公升的容量。 [5] 如前述[1]～[4]中任一項所述之方法，其中，相對於1公升的廢液所添加的硫酸釩溶液為0.05～0.25g。 [6] 如前述[1]～[5]中任一項所述之方法，其中，尖峰溫度為40～130℃。[4] The method according to any one of [1] to [3] above, wherein the waste liquid is distributed to a capacity of 40 liters. [5] The method according to any one of [1] to [4] above, wherein the amount of the vanadium sulfate solution added to 1 liter of waste liquid is 0.05 to 0.25 g. [6] The method according to any one of [1] to [5] above, wherein the peak temperature is 40 to 130°C.
[7] 如前述[1]～[6]中任一項所述之方法，其中，攪拌是利用空氣鼓泡(air bubbling)來實行。 [8] 如前述[1]～[7]中任一項所述之方法，其中，針對包含1.6～10.0重量%的過氧化氫之廢液的分解，在到達尖峰溫度後的靜置時間為5分鐘以上。 [9] 一種再生方法，其將含有硫酸和過氧化氫之廢液再生為工業用硫酸，該再生方法使用了前述[1]～[8]中任一項所述之方法。[7] The method according to any one of [1] to [6] above, wherein the stirring is performed by air bubbling. [8] The method according to any one of [1] to [7] above, wherein for the decomposition of the waste liquid containing 1.6 to 10.0% by weight of hydrogen peroxide, the standing time after reaching the peak temperature is More than 5 minutes. [9] A regeneration method for regenerating a waste liquid containing sulfuric acid and hydrogen peroxide into industrial sulfuric acid, the regeneration method using the method described in any one of [1] to [8].
[10] 一種分解裝置，其可分解含有硫酸和過氧化氫之廢液中的過氧化氫，該裝置具備1個或2個以上可實行分解反應的分解槽； 前述分解槽是具備下述結構而成： 投入用開口部，其用以將廢液及/或硫酸釩投入分解槽內； 攪拌手段，其在分解槽內的分解反應中將廢液進行攪拌； 排出用開口部，其用以將由分解反應所產生的氧氣排出； 溫度計，其測定在分解反應中的廢液的尖峰溫度；及， 冷卻手段，其將分解反應後的廢液進行冷卻。[10] A decomposition device that can decompose hydrogen peroxide in a waste liquid containing sulfuric acid and hydrogen peroxide, the device is equipped with one or more decomposition tanks that can perform decomposition reactions; The aforementioned decomposition tank has the following structure: An opening for input, which is used to put waste liquid and/or vanadium sulfate into the decomposition tank; Stirring means, which stirs the waste liquid in the decomposition reaction in the decomposition tank; The discharge opening is used to discharge the oxygen generated by the decomposition reaction; Thermometer, which measures the peak temperature of the waste liquid in the decomposition reaction; and, Cooling means, which cools the waste liquid after the decomposition reaction.
[11] 如前述[10]所述之裝置，其中，投入分解槽的廢液量為分解槽容量的8成以下。 [12] 如前述[10]或[11]所述之裝置，其中，冷卻手段是藉由冷水進行的外部冷卻。 [13] 如前述[10]～[12]中任一項所述之裝置，其中，該裝置已自動化。 [發明的效果][11] The apparatus described in [10] above, wherein the amount of waste liquid put into the decomposition tank is 80% or less of the capacity of the decomposition tank. [12] The device according to [10] or [11] above, wherein the cooling means is external cooling by cold water. [13] The device according to any one of [10] to [12] above, wherein the device has been automated. [Effects of the invention]
因為本發明的方法不需要大型設備，也不需要昂貴的過氧化氫濃度計、及使用該過氧化氫濃度計的經時性的濃度測定，所以能夠經濟且有效地對於含有硫酸和過氧化氫之廢液中的過氧化氫實行分解處理。 又，因為本發明的方法是以原液的狀態來處理而不用中和或稀釋廢液，所以能夠抑制處理後的溶液的產生量。 並且，本發明的方法藉由將廢液分配為一定量並使用複數個分解槽來處理，即便在過氧化氫為高濃度時，仍能夠安全地處理。 進一步，藉由本發明的裝置，能夠自動地實行上述方法，而能夠簡便且正確地實行連續的過氧化氫分解處理。Because the method of the present invention does not require large-scale equipment, expensive hydrogen peroxide concentration meter, and time-dependent concentration measurement using the hydrogen peroxide concentration meter, it can be economically and effectively applied to sulfuric acid and hydrogen peroxide. The hydrogen peroxide in the waste liquid is decomposed. In addition, since the method of the present invention is to treat the raw liquid without neutralizing or diluting the waste liquid, it is possible to suppress the amount of solution produced after the treatment. In addition, the method of the present invention distributes the waste liquid into a certain amount and uses a plurality of decomposition tanks for processing, so that even when the hydrogen peroxide concentration is high, it can be safely processed. Furthermore, with the apparatus of the present invention, the above-mentioned method can be carried out automatically, and continuous hydrogen peroxide decomposition treatment can be carried out simply and accurately.
以下，基於本發明的適合的實施形態，詳細地說明本發明。 本發明關於一種過氧化氫的分解方法，該過氧化氫是含有硫酸和過氧化氫之廢液中的過氧化氫，並且，前述方法中包含以下步驟：將硫酸釩溶液添加在廢液中並進行攪拌的步驟；在廢液到達尖峰溫度後靜置一定時間的步驟；及，在靜置後進行冷卻的步驟。Hereinafter, the present invention will be described in detail based on suitable embodiments of the present invention. The present invention relates to a method for decomposing hydrogen peroxide. The hydrogen peroxide is hydrogen peroxide in a waste liquid containing sulfuric acid and hydrogen peroxide, and the aforementioned method includes the following steps: adding a vanadium sulfate solution to the waste liquid and A step of stirring; a step of standing for a certain period of time after the waste liquid reaches a peak temperature; and a step of cooling after standing.
又，本發明也關於一種分解裝置，其使用上述方法並可分解含有硫酸和過氧化氫之廢液中的過氧化氫。 該裝置具備1個或2個以上可實行分解反應的分解槽。又，分解槽具備下述結構：投入用開口部，其用以將廢液及/或硫酸釩投入分解槽內；攪拌手段，其在分解槽內的分解反應中將廢液進行攪拌；排出用開口部，其用以將由分解反應所產生的氧氣排出；溫度計，其測定在分解反應中的廢液的尖峰溫度；及，冷卻手段，其將分解反應後的廢液進行冷卻。In addition, the present invention also relates to a decomposition device that can decompose hydrogen peroxide in a waste liquid containing sulfuric acid and hydrogen peroxide by using the above method. The device is equipped with one or more decomposition tanks capable of performing decomposition reactions. In addition, the decomposition tank has the following structure: an opening for input, which is used to put waste liquid and/or vanadium sulfate into the decomposition tank; a stirring means, which agitates the waste liquid during the decomposition reaction in the decomposition tank; The opening is used to discharge the oxygen generated by the decomposition reaction; the thermometer measures the peak temperature of the waste liquid in the decomposition reaction; and the cooling means is used to cool the waste liquid after the decomposition reaction.
在本發明的分解槽中所實行且藉由使硫酸釩與廢液接觸所產生的過氧化氫的分解反應，如下所述： H2 O2 →H2 O+(1/2)O2 (式1) 在式1的反應中，硫酸釩在過氧化氫的分解反應中是作為觸媒來作用，並且硫酸釩本身不會進行反應。該分解反應是發熱反應。The decomposition reaction of hydrogen peroxide carried out in the decomposition tank of the present invention and produced by contacting vanadium sulfate with waste liquid is as follows: H 2 O 2 →H 2 O+(1/2)O 2 (Formula 1) In the reaction of formula 1, vanadium sulfate acts as a catalyst in the decomposition reaction of hydrogen peroxide, and vanadium sulfate itself does not react. This decomposition reaction is an exothermic reaction.
本發明是自投入用開口部將廢液、硫酸釩溶液依序投入分解槽內，並藉由攪拌手段來進行攪拌。In the present invention, the waste liquid and the vanadium sulfate solution are sequentially poured into the decomposition tank from the opening for feeding, and stirred by a stirring means.
在本發明中所使用的廢液含有硫酸和過氧化氫。硫酸的濃度並無特別限制，例如是70重量%左右。過氧化氫的濃度亦無特別限制，較佳是10.0重量%以下，更佳是7.0重量%以下，進一步較佳是1.6～10.0重量%，特佳是1.6～7.0重量%。廢液可包含硫酸和過氧化氫以外的成分。The waste liquid used in the present invention contains sulfuric acid and hydrogen peroxide. The concentration of sulfuric acid is not particularly limited, and is, for example, about 70% by weight. The concentration of hydrogen peroxide is also not particularly limited, and is preferably 10.0% by weight or less, more preferably 7.0% by weight or less, still more preferably 1.6 to 10.0% by weight, and particularly preferably 1.6 to 7.0% by weight. The waste liquid may contain components other than sulfuric acid and hydrogen peroxide.
廢液的種類，只要是在廢液中包含有硫酸和過氧化氫者即可，並無特別限制，可列舉用於半導體的晶圓洗淨的SPM的廢液、化學研磨液等，作為藉由本發明所處理的廢液，較佳是用於半導體的晶圓洗淨的SPM的廢液。 當廢液是用於半導體的晶圓洗淨的SPM的廢液時，每日的廢液產生量並無特別限制，例如是1000～4000公升。 在使用1個分解槽來處理大量的廢液的情況下，尤其當廢液中的過氧化氫為高濃度時，會劇烈地進行分解反應，所以在廢液處理操作時會有發生危險的疑慮。從而，從安全的處理的觀點來看，較佳是分配一定的廢液量並使用複數個分解槽來處理廢液中的過氧化氫，雖然並無特別限制，例如可分配為40公升的容量。藉由分配為一定的廢液量來進行處理，即便過氧化氫為高濃度，仍能夠安全地處理。又，因為各分解槽中的分解反應互為獨立，所以即便其中一個分解槽發生危險，也不會影響到其他分解槽，故能夠將廢液處理操作所伴隨的危險降到最小的程度。The type of waste liquid is not particularly limited as long as the waste liquid contains sulfuric acid and hydrogen peroxide. Examples include SPM waste liquid used for semiconductor wafer cleaning, chemical polishing liquid, etc. The waste liquid processed by the present invention is preferably SPM waste liquid used for semiconductor wafer cleaning. When the waste liquid is the waste liquid of SPM used for semiconductor wafer cleaning, the daily amount of waste liquid generated is not particularly limited, for example, 1,000 to 4,000 liters. In the case of using one decomposition tank to treat a large amount of waste liquid, especially when the hydrogen peroxide in the waste liquid has a high concentration, the decomposition reaction will occur violently, so there is a concern about danger during the waste liquid treatment operation . Therefore, from the viewpoint of safe disposal, it is preferable to allocate a certain amount of waste liquid and use a plurality of decomposition tanks to treat the hydrogen peroxide in the waste liquid, although there is no particular limitation, for example, it can be allocated to a capacity of 40 liters. . By distributing a certain amount of waste liquid for processing, even if the hydrogen peroxide has a high concentration, it can still be safely processed. In addition, because the decomposition reactions in the decomposition tanks are independent of each other, even if one of the decomposition tanks is dangerous, the other decomposition tanks will not be affected, so that the risk associated with the waste liquid treatment operation can be minimized.
用於本發明的硫酸釩溶液，只要是能夠分解廢液中的過氧化氫者，其溶媒並無特別限制。 硫酸釩溶液的使用量，並無特別限制，相對於1公升的要進行處理的廢液，較佳是0.05～0.25g。若超過0.25g，會過剩地促進過氧化氫的分解，而會有在廢液處理操作時發生危險的疑慮。另一方面，若低於0.05g，過氧化氫的分解反應會無法充分地進行。The vanadium sulfate solution used in the present invention is not particularly limited as long as it can decompose hydrogen peroxide in the waste liquid. The amount of the vanadium sulfate solution used is not particularly limited, and it is preferably 0.05 to 0.25 g relative to 1 liter of waste liquid to be processed. If it exceeds 0.25 g, the decomposition of hydrogen peroxide will be excessively promoted, and there is a concern that it will be dangerous during the waste liquid treatment operation. On the other hand, if it is less than 0.05 g, the decomposition reaction of hydrogen peroxide may not proceed sufficiently.
用於本發明的分解槽，只要是耐強酸性者，其材質並無特別限定，例如能夠是內襯有樹脂而成的金屬製、內襯有玻璃而成的金屬製及氟樹脂製等，較佳是內襯有玻璃而成的金屬製。 分解槽的形狀，只要不會妨礙含有硫酸和過氧化氫之廢液中的過氧化氫的分解，並無特別限定，可列舉例如：圓柱狀、箱狀等，從攪拌的容易性的觀點來看，較佳是圓柱狀。 分解槽的尺寸，只要能夠安全地實行含有硫酸和過氧化氫之廢液中的過氧化氫的分解即可，並無特別限定，可列舉例如：φ300mm×H700mm且容量換算約為50公升者。被投入分解槽內的廢液量，只要是能夠安全地實行處理的量即可，並無特別限制，較佳是分解槽容量的8成以下，例如是40公升。 可投入廢液與硫酸釩溶液之投入用開口部，可以相同也可以不同。該投入用開口部能夠開關。The material of the decomposition tank used in the present invention is not particularly limited as long as it is strong acid resistant. For example, it can be made of metal lined with resin, metal lined with glass, or fluororesin. It is preferably made of metal lined with glass. The shape of the decomposition tank is not particularly limited as long as it does not hinder the decomposition of hydrogen peroxide in the waste liquid containing sulfuric acid and hydrogen peroxide. Examples include cylindrical and box shapes. From the standpoint of ease of stirring Seen, it is preferably cylindrical. The size of the decomposition tank is not particularly limited as long as it can safely decompose the hydrogen peroxide in the waste liquid containing sulfuric acid and hydrogen peroxide. For example, φ300mm×H700mm and the capacity conversion is about 50 liters. The amount of waste liquid thrown into the decomposition tank is not particularly limited as long as it can be safely processed, and it is preferably 80% or less of the capacity of the decomposition tank, for example, 40 liters. The openings for inputting waste liquid and vanadium sulfate solution may be the same or different. The opening for input can be opened and closed.
用於本發明的攪拌手段，只要是能夠使廢液與硫酸釩溶液效率良好地接觸而促進廢液中的過氧化氫的分解反應者即可，並無特別限制，可列舉攪拌機、空氣鼓泡(air bubbling)等。因為廢液中包含硫酸，所以當為使用金屬的攪拌手段時，會產生由於硫酸而造成金屬的溶解或腐蝕等的疑慮。從而，從不使用金屬的觀點來看，較佳是空氣鼓泡。 使用空氣鼓泡作為攪拌手段時，空氣的流通速度，只要能夠使廢液與硫酸釩溶液效率良好地接觸而促進廢液中的過氧化氫的分解反應，且為可安全地實行的流通速度即可，並無特別限制。又，若持續地實行空氣鼓泡，會有分解反應變得劇烈的疑慮，故較佳是間歇性地實行。The stirring means used in the present invention is not particularly limited as long as it can efficiently contact the waste liquid with the vanadium sulfate solution and promote the decomposition reaction of hydrogen peroxide in the waste liquid. Examples include agitator and air bubbling. (air bubbling) and so on. Because the waste liquid contains sulfuric acid, when a metal stirring means is used, there is a concern that the sulfuric acid may cause metal dissolution or corrosion. Therefore, from the viewpoint of not using metal, air bubbling is preferable. When air bubbling is used as a stirring means, the air flow rate is such that the waste liquid can be efficiently contacted with the vanadium sulfate solution to promote the decomposition reaction of hydrogen peroxide in the waste liquid, and the flow rate can be safely performed. Yes, there are no special restrictions. In addition, if air bubbling is performed continuously, the decomposition reaction may become violent, so it is preferable to perform it intermittently.
由分解反應所產生的氧氣，可藉由排出用開口部被排出。將氧氣排出的排出用開口部，可以與投入廢液及/或硫酸釩溶液之排出用開口部相同，亦可以不同。The oxygen generated by the decomposition reaction can be exhausted through the exhaust opening. The discharge opening through which oxygen is discharged may be the same as or different from the discharge opening through which the waste liquid and/or vanadium sulfate solution is input.
本發明藉由溫度計測定分解反應中的廢液的尖峰溫度後，會靜置一定時間。 在本發明中所測定的廢液的尖峰溫度，表示廢液的最高溫度，該廢液是被伴隨過氧化氫的分解反應所產生的熱量加熱而升溫，當廢液的溫度開始下降時，將開始下降前的溫度視為廢液的最高溫度。In the present invention, after measuring the peak temperature of the waste liquid in the decomposition reaction with a thermometer, it will stand for a certain period of time. The peak temperature of the waste liquid measured in the present invention represents the highest temperature of the waste liquid. The waste liquid is heated by the heat generated by the decomposition reaction of hydrogen peroxide. When the temperature of the waste liquid starts to drop, the The temperature before the start of the drop is regarded as the maximum temperature of the waste liquid.
用於本發明的廢液的溫度的測定手段，並無特別限制，較佳是被氟樹脂等所包覆而成的熱電偶偵測器。 尖峰溫度會與廢液中的過氧化氫濃度呈正相關，例如過氧化氫為2.0～8.0重量%時，為40～130℃。從安全地實行分解反應的觀點來看，尖峰溫度較佳是80℃以下。The measuring method of the temperature of the waste liquid used in the present invention is not particularly limited, and a thermocouple detector coated with a fluororesin or the like is preferable. The peak temperature will have a positive correlation with the concentration of hydrogen peroxide in the waste liquid. For example, when the hydrogen peroxide is 2.0-8.0% by weight, it is 40-130°C. From the viewpoint of safely performing the decomposition reaction, the peak temperature is preferably 80°C or lower.
即便在靜置步驟中，過氧化氫的分解反應仍會持續進行。根據實驗上已知的尖峰溫度、與減少至特定的過氧化氫濃度的靜置時間的關係，就能夠僅利用靜置來使過氧化氫降低至特定的濃度。藉由該步驟，就變得不需要用以持續測定廢液中的過氧化氫濃度的昂貴的濃度計，並且能夠經濟且有效地控制過氧化氫的分解反應。 在一態樣中，當廢液中的過氧化氫濃度為1.6～10.0重量%時，靜置時間為5分鐘以上。Even in the standing step, the decomposition reaction of hydrogen peroxide continues. Based on the experimentally known relationship between the peak temperature and the standing time to reduce to a specific hydrogen peroxide concentration, it is possible to reduce the hydrogen peroxide to a specific concentration only by standing. With this step, an expensive concentration meter for continuously measuring the concentration of hydrogen peroxide in the waste liquid becomes unnecessary, and the decomposition reaction of hydrogen peroxide can be controlled economically and effectively. In one aspect, when the concentration of hydrogen peroxide in the waste liquid is 1.6 to 10.0% by weight, the standing time is 5 minutes or more.
本發明在靜置後，會藉由冷卻手段來進行冷卻。 在本發明中所使用的冷卻，是在靜置之後所實行者，其主要具有使分解反應完全結束，並使廢液的溫度降低至安全的溫度的功能。在進行靜置期間，分解反應仍會持續進行，所以若在靜置期間實行冷卻，因為可能會造成分解反應在實行至特定的過氧化氫濃度前就結束的情況，所以在靜置期間不實行冷卻，而是在自靜置完成後起才開始進行冷卻。The present invention will be cooled by cooling means after standing still. The cooling used in the present invention is performed after standing still, and mainly has the function of completely ending the decomposition reaction and lowering the temperature of the waste liquid to a safe temperature. During the standing period, the decomposition reaction will continue, so if cooling is performed during the standing period, the decomposition reaction may end before the specific hydrogen peroxide concentration is implemented, so it is not performed during the standing period. Cooling, but starting to cool after the completion of standing.
用於本發明的冷卻手段，只要是能夠在不改變廢液的組成的情況下，能夠將過氧化氫的分解反應已結束的廢液降低至安全的溫度者即可，並無特別限制，較佳是藉由冷水進行的外部冷卻。再者，當藉由冷水進行外部冷卻時，分解槽能夠以冷卻水可流經分解槽的外裝的方式來具有雙槽結構。又，若是在分解層的內側使用玻璃內襯，可提高冷卻效率而較佳。 在施行本發明的方法後所獲得的液體中的過氧化氫濃度，較佳是0.5重量%以下，更佳是0.1重量%以下。The cooling means used in the present invention is not particularly limited as long as it can reduce the waste liquid whose decomposition reaction of hydrogen peroxide has been completed to a safe temperature without changing the composition of the waste liquid. The best is external cooling by cold water. Furthermore, when external cooling is performed by cold water, the decomposition tank can have a double tank structure so that cooling water can flow through the exterior of the decomposition tank. Moreover, if a glass lining is used inside the decomposition layer, the cooling efficiency can be improved, which is preferable. The concentration of hydrogen peroxide in the liquid obtained after performing the method of the present invention is preferably 0.5% by weight or less, more preferably 0.1% by weight or less.
進一步，本發明關於一種再生方法，其使用本發明的方法來將含有硫酸和過氧化氫之廢液再生為工業用硫酸。Further, the present invention relates to a regeneration method that uses the method of the present invention to regenerate waste liquid containing sulfuric acid and hydrogen peroxide into industrial sulfuric acid.
本發明的方法，在一態樣中，能夠使用已自動化的本發明的裝置來實行。 [實施例]The method of the present invention, in one aspect, can be implemented using an automated device of the present invention. [Example]
繼而，藉由以下所述之實施例和比較例，進一步詳細地說明本發明的過氧化氫的分解方法及使用該方法的裝置，但是本發明並未限定於此。Then, the method for decomposing hydrogen peroxide of the present invention and the device using the method are described in further detail by the following examples and comparative examples, but the present invention is not limited to this.
以每日2800公升的包含硫酸和過氧化氫之廢液(硫酸70重量%、過氧化氫7重量%以下)作為處理對象，準備具有第1圖的結構之過氧化氫分解裝置1(關東工程(Kanto engineering)股份有限公司製造)，該裝置包含6個分解槽，該廢液是自製造半導體的晶圓洗淨步驟所排放出。該過氧化氫分解裝置，可被收納在PVC(聚氯乙烯)樹脂製的箱體中，其外徑約為D1200mm×W3000mm×H2000mm， 各分解槽的容量為23公升。 將1個分解槽的一批次的處理時間設定為1小時，並且將6個分解槽全部設定為自動連續運轉。1個分解槽的一批次的自動處理流程如下所述。當裝置開始自動運轉，會自廢水處理槽投入廢液，並且會自分解劑槽投入3g的硫酸釩。在分解槽中，間歇性地實行空氣鼓泡，並測定到溫度為40℃後，會使空氣鼓泡完全地停止。並且在測定到尖峰溫度後，使分解槽靜置15分鐘。在靜置後，使冷卻水流通，冷卻分解槽的外部直到分解槽中的液溫成為35℃為止。冷卻後，使分解後的包含硫酸釩之廢液自分解槽排出，並儲藏在儲存槽(holding tank)中。又，亦會另外將冷卻水排出。分解後的廢液的過氧化氫濃度為0.1重量%以下。 利用6個槽來實行上述的運轉，24小時可完成約3000公升的處理。Take 2,800 liters of waste liquid containing sulfuric acid and hydrogen peroxide (70% by weight of sulfuric acid and less than 7% by weight of hydrogen peroxide) per day as the treatment object, and prepare the hydrogen peroxide decomposition device 1 with the structure of Figure 1 (Kanto Engineering) (Manufactured by Kanto Engineering Co., Ltd.), the device contains 6 decomposition tanks, and the waste liquid is discharged from the wafer cleaning step for manufacturing semiconductors. This hydrogen peroxide decomposition device can be housed in a box made of PVC (polyvinyl chloride) resin. Its outer diameter is approximately D1200mm×W3000mm×H2000mm, and the capacity of each decomposition tank is 23 liters. The processing time of one batch of 1 decomposition tank is set to 1 hour, and all the 6 decomposition tanks are set to automatic continuous operation. The automatic processing flow for one batch of 1 decomposition tank is as follows. When the device starts to operate automatically, waste liquid will be poured from the waste water treatment tank, and 3g of vanadium sulfate will be poured from the decomposer tank. In the decomposition tank, air bubbling is performed intermittently, and when the temperature is measured to be 40°C, the air bubbling is completely stopped. And after the peak temperature is measured, the decomposition tank is allowed to stand for 15 minutes. After standing still, the cooling water was circulated to cool the outside of the decomposition tank until the liquid temperature in the decomposition tank reached 35°C. After cooling, the decomposed waste liquid containing vanadium sulfate is discharged from the decomposition tank and stored in a holding tank. In addition, cooling water is also discharged separately. The hydrogen peroxide concentration of the decomposed waste liquid is 0.1% by weight or less. Using 6 tanks to perform the above-mentioned operation, about 3000 liters of processing can be completed in 24 hours.
1:過氧化氫分解裝置 2:分解槽 3:投入用開口部 4:攪拌手段 5:排出用開口部 6:溫度計 7:冷卻手段1: Hydrogen peroxide decomposition device 2: decomposition tank 3: Opening for input 4: Stirring means 5: Opening for discharge 6: Thermometer 7: cooling method
第1圖顯示了本發明的過氧化氫分解裝置的分解槽的結構。Figure 1 shows the structure of the decomposition tank of the hydrogen peroxide decomposition device of the present invention.
2 國內寄存資訊 (請依寄存機構、日期、號碼順序註記) 無 3 國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記) 無2 Domestic deposit information (please note in the order of deposit institution, date and number) no 3 Foreign hosting information (please note in the order of hosting country, institution, date and number) no
1:過氧化氫分解裝置 1: Hydrogen peroxide decomposition device
2:分解槽 2: decomposition tank
3:投入用開口部 3: Opening for input
4:攪拌手段 4: Stirring means
5:排出用開口部 5: Opening for discharge
6:溫度計 6: Thermometer
7:冷卻手段 7: cooling method
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