TWI623493B - Tmah solution decomposition apparatus - Google Patents
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Abstract
本發明揭露一種四甲基氫氧化銨(TMAH)溶液的分解方法及其分解裝置，主要透過混合四甲基氫氧化銨溶液、氧化劑以及觸媒，達到分解四甲基氫氧化銨的目的。氧化劑包括一次氯酸根或一次氯酸鹽，四甲基氫氧化銨溶液會與氧化劑反應，而觸媒則會吸附反應過程中產生的氧原子。觸媒吸附的氧原子會進一步參與反應，藉此將四甲基氫氧化銨分解成氮氣及醇類。透過本發明所提出的四甲基氫氧化銨溶液的分解方法，可使四甲基氫氧化銨溶液中的四甲基氫氧化銨去除率大於99%。 The invention discloses a decomposition method of a tetramethylammonium hydroxide (TMAH) solution and a decomposition device thereof, which mainly achieve the purpose of decomposing tetramethylammonium hydroxide by mixing a tetramethylammonium hydroxide solution, an oxidant and a catalyst. The oxidizing agent includes primary chlorate or primary chlorate, and the tetramethylammonium hydroxide solution reacts with the oxidizing agent, and the catalyst adsorbs oxygen atoms generated during the reaction. The oxygen atoms adsorbed by the catalyst further participate in the reaction, thereby decomposing tetramethylammonium hydroxide into nitrogen and alcohol. The tetramethylammonium hydroxide removal rate in the tetramethylammonium hydroxide solution can be made greater than 99% by the decomposition method of the tetramethylammonium hydroxide solution proposed by the present invention.
Description
本發明有關一種四甲基氫氧化銨(TMAH)溶液的分解方法及其分解裝置，主要是將四甲基氫氧化銨溶液、氧化劑以及觸媒混合，以產生氮氣以及醇類。 The invention relates to a method for decomposing a tetramethylammonium hydroxide (TMAH) solution and a decomposition device thereof, which mainly comprises mixing a tetramethylammonium hydroxide solution, an oxidizing agent and a catalyst to generate nitrogen gas and an alcohol.
半導體製程中常採用四甲基氫氧化銨(TMAH，tetramethyl ammonium hydroxide)去除光阻，並且產生含四甲基氫氧化銨的廢水。由於四甲基氫氧化銨具有毒性，廢水不可直接排放，一般的作法是使用微生物或漂白水將廢水中的四甲基氫氧化銨分解後再排放。微生物分解四甲基氫氧化銨的速率慢，且須使用大面積的場地，無法符合目前半導體產業的需求。 In the semiconductor process, tetramethyl ammonium hydroxide (TMAH) is often used to remove photoresist and produce wastewater containing tetramethylammonium hydroxide. Since tetramethylammonium hydroxide is toxic, wastewater cannot be directly discharged. It is common practice to use microorganisms or bleach to decompose tetramethylammonium hydroxide in wastewater and then discharge it. Microbial decomposition of tetramethylammonium hydroxide is slow and requires a large area of space to meet the needs of the current semiconductor industry.
使用漂白水分解四甲基氫氧化銨，一般是採用折點加氯法，透過反覆在四甲基氫氧化銨廢水中加入次氯酸，並控制反應時的酸鹼值在PH6至PH7之間，來達成分解四甲基氫氧化銨的目的。然而折點加氯法須耗用大量的次氯酸，且反應過程中因為要不斷的加次氯酸，酸鹼值區間的控制難度高。此外，四甲基氫氧化銨與次氯酸反應氯化之後，與水作用又會還原成氨氮形式，大大的降低了分解效率，其分解效率約只有5%至10%。 The use of bleach to decompose tetramethylammonium hydroxide is generally carried out by adding the hypochlorous acid to the tetramethylammonium hydroxide wastewater by a fulcrum and chlorination method, and controlling the pH value between PH6 and PH7. To achieve the purpose of decomposing tetramethylammonium hydroxide. However, the chlorination method requires a large amount of hypochlorous acid, and the control of the pH range is difficult because of the continuous addition of hypochlorous acid during the reaction. In addition, after the reaction of tetramethylammonium hydroxide with hypochlorous acid chlorination, the action with water is reduced to the form of ammonia nitrogen, which greatly reduces the decomposition efficiency, and the decomposition efficiency is only about 5% to 10%.
本發明之一目的，在於提供一種四甲基氫氧化銨溶液的分解方法，主要是將四甲基氫氧化銨溶液、氧化劑以及觸媒混合，利用觸媒吸附四甲基氫氧化銨溶液與氧化劑反應後所產生的氧原子，以產生氮氣以及醇類。透過此方法可使四甲基氫氧化銨溶液中的四甲基氫氧化銨去除率大於99%，並且可將半導體製程所產生的四甲基氫氧化銨廢水中的四甲基氫氧化銨濃度由4000ppm以下降至1ppm以下。 An object of the present invention is to provide a method for decomposing a tetramethylammonium hydroxide solution, which mainly comprises mixing a tetramethylammonium hydroxide solution, an oxidizing agent and a catalyst, and adsorbing a tetramethylammonium hydroxide solution and an oxidizing agent by using a catalyst. The oxygen atoms produced after the reaction produce nitrogen and alcohol. By this method, the tetramethylammonium hydroxide removal rate in the tetramethylammonium hydroxide solution can be greater than 99%, and the concentration of tetramethylammonium hydroxide in the tetramethylammonium hydroxide wastewater produced by the semiconductor process can be obtained. It is reduced from below 4000 ppm to below 1 ppm.
本發明之另一目的，在於將本發明所述之四甲基氫氧化銨溶液的分解方法，應用於一四甲基氫氧化銨溶液分解裝置。四甲基氫氧化銨溶液分解裝置主要包括一混合槽、至少一傳輸管及一觸媒槽，其中混合槽透過傳輸管連接觸媒槽。混合槽用以混合四甲基氫氧化銨溶液及氧化劑，並產生N(CH3)3ClOH，觸媒槽則用以容置一觸媒，並透過傳輸管由混合槽接收N(CH3)3ClOH及四甲基氫氧化銨溶液中的水分子。水分子與N(CH3)3ClOH反應產生NH(CH3)3OH，而觸媒則吸附水分子與N(CH3)3ClOH反應後產生的氧原子。NH(CH3)3OH、觸媒所吸附的氧原子以及水分子會反應產生氮氣以及醇類。此外四甲基氫氧化銨溶液、N(CH3)3ClOH、NH(CH3)3OH、氧化劑及/或鹽酸可經由傳輸管在混合槽以及觸媒槽之間流動，以達到混拌的效果，並增加氮氣以及醇類產生的效率。 Another object of the present invention is to apply a method for decomposing a tetramethylammonium hydroxide solution according to the present invention to a tetramethylammonium hydroxide solution decomposition apparatus. The tetramethylammonium hydroxide solution decomposition device mainly comprises a mixing tank, at least one transfer tube and a catalyst tank, wherein the mixing tank is connected to the catalyst tank through the transfer tube. The mixing tank is used for mixing the tetramethylammonium hydroxide solution and the oxidant, and generates N(CH3)3ClOH. The catalyst tank is used for accommodating a catalyst, and the N(CH3)3ClOH and the fourth are received from the mixing tank through the transfer tube. Water molecules in methylammonium hydroxide solution. The water molecules react with N(CH3)3ClOH to produce NH(CH3)3OH, while the catalyst adsorbs the oxygen atoms produced by the reaction of water molecules with N(CH3)3ClOH. NH(CH3)3OH, the oxygen atoms adsorbed by the catalyst, and water molecules react to produce nitrogen and alcohol. In addition, a tetramethylammonium hydroxide solution, N(CH3)3ClOH, NH(CH3)3OH, an oxidizing agent and/or a hydrochloric acid may flow between the mixing tank and the catalyst tank through a transfer pipe to achieve the effect of mixing and increase The efficiency of nitrogen and alcohol production.
為達到上述目的，本發明提供一種四甲基氫氧化銨溶液的分解方法，包括以下步驟：混合一四甲基氫氧化銨溶液、一氧化劑及一觸媒，其中 氧化劑包括一次氯酸根或一次氯酸鹽，而觸媒則吸附四甲基氫氧化銨溶液與氧化劑反應後所產生的一氧原子；及產生一氮氣及一醇類。 In order to achieve the above object, the present invention provides a method for decomposing a tetramethylammonium hydroxide solution, comprising the steps of: mixing a tetramethylammonium hydroxide solution, an oxidizing agent and a catalyst, wherein The oxidizing agent includes primary chlorate or primary chlorate, and the catalyst adsorbs an oxygen atom generated by the reaction of the tetramethylammonium hydroxide solution with the oxidizing agent; and generates a nitrogen gas and an alcohol.
為達到上述目的，本發明提供一種四甲基氫氧化銨溶液的分解裝置，包括：一混合槽，用以混合一四甲基氫氧化銨溶液及一氧化劑，以產生一N(CH3)3ClOH，其中四甲基氫氧化銨溶液包括一四甲基氫氧化銨及一水分子，而氧化劑包括一次氯酸根或一次氯酸鹽；至少一傳輸管，連接混合槽；及一觸媒槽，用以容置一觸媒，並連接傳輸管，其中觸媒槽透過傳輸管由混合槽接收N(CH3)3ClOH及水分子，使得水分子與N(CH3)3ClOH反應產生一NH(CH3)3OH，且觸媒吸附水分子與N(CH3)3ClOH反應產生的一氧原子，並使NH(CH3)3OH、觸媒所吸附的氧原子以及水分子反應產生一氮氣以及一醇類。 In order to achieve the above object, the present invention provides a decomposition apparatus for a tetramethylammonium hydroxide solution, comprising: a mixing tank for mixing a tetramethylammonium hydroxide solution and an oxidizing agent to produce a N(CH3)3ClOH, Wherein the tetramethylammonium hydroxide solution comprises monomethylammonium hydroxide and one water molecule, and the oxidant comprises primary chlorate or primary chlorate; at least one transfer tube is connected to the mixing tank; and a catalyst tank is used for Storing a catalyst and connecting the transfer tube, wherein the catalyst tank receives N(CH3)3ClOH and water molecules from the mixing tank through the transfer tube, so that the water molecules react with N(CH3)3ClOH to generate an NH(CH3)3OH, and The catalyst adsorbs an oxygen atom generated by the reaction of water molecules with N(CH3)3ClOH, and reacts NH(CH3)3OH, an oxygen atom adsorbed by the catalyst, and water molecules to produce a nitrogen gas and an alcohol.
在本發明分解方法一實施例中，其中四甲基氫氧化銨溶液包括一四甲基氫氧化銨及一水分子。 In an embodiment of the decomposition method of the present invention, the tetramethylammonium hydroxide solution comprises monomethylammonium hydroxide and one water molecule.
在本發明分解方法一實施例中，其中還包括以下步驟：四甲基氫氧化銨溶液、氧化劑以及觸媒混合後，產生一NH(CH3)3OH；及觸媒所吸附的氧原子、NH(CH3)3OH以及水分子反應產生氮氣以及醇類。 In an embodiment of the decomposition method of the present invention, the method further comprises the steps of: mixing a tetramethylammonium hydroxide solution, an oxidizing agent and a catalyst to produce an NH(CH3)3OH; and an oxygen atom adsorbed by the catalyst, NH ( CH3) 3OH and water molecules react to produce nitrogen and alcohol.
在本發明分解方法一實施例中，還包括以下步驟：混合四甲基氫氧化銨溶液及氧化劑，以產生一N(CH3)3ClOH；加入觸媒，使觸媒、N(CH3)3ClOH與水分子混合，並產生一NH(CH3)3OH，且觸媒吸附N(CH3)3ClOH與水分子反應後所產生的氧原子；及觸媒所吸附的氧原子、NH(CH3)3OH及水分子反應產生氮氣以及醇類。 In an embodiment of the decomposition method of the present invention, the method further comprises the steps of: mixing a tetramethylammonium hydroxide solution and an oxidizing agent to produce a N(CH3)3ClOH; adding a catalyst to cause a catalyst, N(CH3)3ClOH and water. The molecules are mixed and produce a NH(CH3)3OH, and the catalyst adsorbs the oxygen atoms generated by the reaction of N(CH3)3ClOH with water molecules; and the oxygen atoms, NH(CH3)3OH and water molecules adsorbed by the catalyst Nitrogen and alcohol are produced.
在本發明分解方法一實施例中，還包括以下步驟：四甲基氫氧化銨溶液、氧化劑以及觸媒混合後，產生一NH(CH3)3OH及一鹽酸；及加入一鹼，使鹼與鹽酸酸鹼中和。 In an embodiment of the decomposition method of the present invention, the method further comprises the steps of: mixing a tetramethylammonium hydroxide solution, an oxidizing agent and a catalyst to produce a NH(CH3)3OH and a hydrochloric acid; and adding a base to make the alkali and the hydrochloric acid. Acid-base neutralization.
在本發明分解方法一實施例中，其中鹼為氫氧化鈉。 In an embodiment of the decomposition method of the present invention, wherein the base is sodium hydroxide.
在本發明分解方法一實施例中，其中觸媒包括碳元素或活性碳。 In an embodiment of the decomposition method of the present invention, the catalyst comprises carbon or activated carbon.
在本發明分解方法一實施例中，其中觸媒具導電性且不會與四甲基氫氧化銨溶液與氧化劑反應後產生的氧原子產生化學反應。 In an embodiment of the decomposition method of the present invention, the catalyst is electrically conductive and does not chemically react with oxygen atoms generated after the reaction of the tetramethylammonium hydroxide solution with the oxidizing agent.
在本發明分解方法一實施例中，其中氧化劑的用量為所須莫爾當量數的1至1.2倍。 In an embodiment of the decomposition method of the present invention, the oxidizing agent is used in an amount of from 1 to 1.2 times the number of moles required.
在本發明分解方法一實施例中，其中氧化劑包括次氯酸、次氯酸鈉或次氯酸鈣。 In an embodiment of the decomposition method of the present invention, wherein the oxidizing agent comprises hypochlorous acid, sodium hypochlorite or calcium hypochlorite.
在本發明分解裝置一實施例中，其中N(CH3)3ClOH、觸媒與水分子接觸後，產生NH(CH3)3OH及一鹽酸。 In an embodiment of the decomposition apparatus of the present invention, wherein N(CH3)3ClOH and the catalyst are contacted with water molecules, NH(CH3)3OH and monohydrochloric acid are produced.
在本發明分解裝置一實施例中，其中觸媒包括碳元素或活性碳。 In an embodiment of the decomposition apparatus of the present invention, the catalyst comprises carbon or activated carbon.
在本發明分解裝置一實施例中，其中混合槽或觸媒槽還用以接收一鹼與鹽酸酸鹼中和，使混合槽或觸媒槽中的酸鹼值大於PH7。 In an embodiment of the decomposition apparatus of the present invention, the mixing tank or the catalyst tank is further configured to receive a base and neutralize the acid and alkali to make the pH value in the mixing tank or the catalyst tank greater than PH7.
在本發明分解裝置一實施例中，其中傳輸管在混合槽及觸媒槽之間形成迴路，而四甲基氫氧化銨溶液、N(CH3)3ClOH、NH(CH3)3OH或氧化劑則經由傳輸管在混合槽以及觸媒槽之間流動。 In an embodiment of the decomposition apparatus of the present invention, wherein the transfer tube forms a loop between the mixing tank and the catalyst tank, and the tetramethylammonium hydroxide solution, N(CH3)3ClOH, NH(CH3)3OH or the oxidant is transmitted. The tube flows between the mixing tank and the catalyst tank.
20‧‧‧四甲基氫氧化銨溶液的分解裝置 20‧‧‧Decomposition device for tetramethylammonium hydroxide solution
21‧‧‧混合槽 21‧‧‧ mixing tank
211‧‧‧輸入端 211‧‧‧ input
22‧‧‧觸媒槽 22‧‧‧catalyst slot
221‧‧‧輸入管 221‧‧‧Input tube
23‧‧‧觸媒 23‧‧‧ Catalyst
24‧‧‧傳輸管 24‧‧‧Transmission tube
第1圖：為本發明四甲基氫氧化銨溶液的分解方法一實施例的步驟流程圖。 Fig. 1 is a flow chart showing the steps of an embodiment of the method for decomposing a tetramethylammonium hydroxide solution of the present invention.
第2圖：為本發明四甲基氫氧化銨溶液的分解裝置一實施例的構造示意圖。 Fig. 2 is a schematic view showing the structure of an embodiment of a decomposition apparatus for a tetramethylammonium hydroxide solution of the present invention.
雖然已透過舉例方式在圖式中描述了本發明的具體實施方式，並在本文中對其作了詳細的說明，但是本發明還允許有各種修改和替換形式。本發明之圖式內容可為不等比例，圖式及其詳細的描述僅為特定型式的揭露，並不為本發明的限制，相反的，依據本發明的專利範圍之精神和範圍內，進行修改、均等構件及其置換，皆為本發明所涵蓋的範圍。 While the invention has been described by way of illustrations in the drawings The drawings and the scope of the present invention are to be construed as being Modifications, equivalent components, and permutations thereof are within the scope of the invention.
請參閱第1圖，為本發明四甲基氫氧化銨溶液的分解方法一實施例的步驟流程圖。如圖所示，本發明所述的分解方法可包括步驟S101及S103。混合四甲基氫氧化銨溶液、氧化劑以及觸媒，其中氧化劑包括次氯酸根或次氯酸鹽，觸媒用以吸附四甲基氫氧化銨溶液與氧化劑反應後所產生的氧原子，如步驟S101所示。 Please refer to FIG. 1 , which is a flow chart showing the steps of an embodiment of a method for decomposing a tetramethylammonium hydroxide solution of the present invention. As shown, the decomposition method of the present invention may include steps S101 and S103. Mixing a tetramethylammonium hydroxide solution, an oxidizing agent, and a catalyst, wherein the oxidizing agent includes hypochlorite or hypochlorite, and the catalyst is used to adsorb oxygen atoms generated by reacting the tetramethylammonium hydroxide solution with the oxidizing agent, as in the step S101 is shown.
本發明所述的四甲基氫氧化銨溶液包括四甲基氫氧化銨(TMAH，N(CH3)4OH)及水分子。在本發明一實施例中，四甲基氫氧化銨溶液可以是半導體製程所產生的含四甲基氫氧化銨的廢水。 The tetramethylammonium hydroxide solution of the present invention comprises tetramethylammonium hydroxide (TMAH, N(CH3)4OH) and water molecules. In an embodiment of the invention, the tetramethylammonium hydroxide solution may be a wastewater containing tetramethylammonium hydroxide produced by a semiconductor process.
本發明所述的觸媒，可以是具有導電性，且不會與四甲基氫氧化銨溶液與氧化劑反應後所產生的氧原子產生化學反應的物質。在本發明一實施例中，觸媒包括碳元素或活性碳，其中活性碳為本發明一較佳的實施例。 活性碳具有較大的表面積，其吸附氧原子的效率及數量皆較佳，因此使用活性碳可提升本發明所述的分解方法的反應速率。 The catalyst according to the present invention may be one which is electrically conductive and does not chemically react with oxygen atoms generated after the reaction of the tetramethylammonium hydroxide solution with the oxidizing agent. In an embodiment of the invention, the catalyst comprises carbon or activated carbon, wherein the activated carbon is a preferred embodiment of the invention. Activated carbon has a large surface area, and its efficiency and quantity of adsorbing oxygen atoms are preferred, so the use of activated carbon can increase the reaction rate of the decomposition method of the present invention.
四甲基氫氧化銨溶液、氧化劑以及觸媒混合後，會產生氮氣以及醇類，如步驟S103所示。具體來說，四甲基氫氧化銨溶液、氧化劑以及觸媒混合後，會產生NH(CH3)3OH(三甲基氫氧化銨)，而觸媒則會吸附氧原子，例如四甲基氫氧化銨溶液與氧化劑反應產生NH(CH3)3OH及氧原子，而觸媒則吸附四甲基氫氧化銨溶液與氧化劑反應後所產生的氧原子。而後觸媒所吸附的氧原子會與NH(CH3)3OH以及四甲基氫氧化銨溶液中的水分子反應，並產生氮氣以及醇類，如此一來將可有效分解四甲基氫氧化銨。 After the tetramethylammonium hydroxide solution, the oxidizing agent, and the catalyst are mixed, nitrogen gas and alcohol are generated as shown in step S103. Specifically, after the tetramethylammonium hydroxide solution, the oxidizing agent, and the catalyst are mixed, NH(CH3)3OH (trimethylammonium hydroxide) is generated, and the catalyst adsorbs oxygen atoms, such as tetramethyl hydroxide. The ammonium solution reacts with the oxidant to produce NH(CH3)3OH and an oxygen atom, and the catalyst adsorbs the oxygen atoms generated by the reaction of the tetramethylammonium hydroxide solution with the oxidant. The oxygen atoms adsorbed by the catalyst react with water molecules in NH(CH3)3OH and tetramethylammonium hydroxide solutions to produce nitrogen and alcohol, which will effectively decompose tetramethylammonium hydroxide.
在本發明一實施例中，可以先將四甲基氫氧化銨溶液及氧化劑混合，之後再加入觸媒，請參考下列的化學化學反應式：N(CH3)4OH+HOCl → N(CH3)3ClOH+CH3OH….……(1) N(CH3)3ClOH+H2O+C* → NH(CH3)3OH+HCl+C*O….……(2) 3C*O+2NH(CH3)3OH+H2O → N2+6CH3OH+3C*….……(3)舉例來說，可先將四甲基氫氧化銨溶液與氧化劑次氯酸混合，使四甲基氫氧化銨(TMAH，N(CH3)4OH)與次氯酸反應，並產生N(CH3)3ClOH(一氯三甲基氫氧化銨)，如化學反應式(1)所示。接著加入觸媒，使觸媒、N(CH3)3ClOH以及四甲基氫氧化銨溶液中的水分子接觸或混合，以產生NH(CH3)3OH(三甲基氫氧化銨)及氧原子，而觸媒則會吸附氧原子，例如N(CH3)3ClOH與水分子反應產生NH(CH3)3OH以及氧原子，而觸媒則吸附N(CH3)3ClOH與水分子反應所產生的氧原子，如化學反應式(2)所示。而後 觸媒所吸附的氧原子會進一步與NH(CH3)3OH及水分子反應，並產生氮氣以及醇類，如化學反應式(3)所示。 In an embodiment of the present invention, the tetramethylammonium hydroxide solution and the oxidizing agent may be mixed first, and then the catalyst is added. Please refer to the following chemical chemical reaction formula: N(CH3)4OH+HOCl→N(CH3)3ClOH +CH3OH..........(1) N(CH3)3ClOH+H2O+C* → NH(CH3)3OH+HCl+C*O..........(2) 3C*O+2NH(CH3)3OH+H2O → N2+6CH3OH+3C*.... (3) For example, the tetramethylammonium hydroxide solution may be mixed with the oxidizing agent hypochlorous acid to make tetramethylammonium hydroxide (TMAH, N(CH3)4OH). It reacts with hypochlorous acid and produces N(CH3)3ClOH (monochlorotrimethylammonium hydroxide) as shown in the chemical reaction formula (1). Next, a catalyst is added to contact or mix the water molecules in the catalyst, N(CH3)3ClOH and tetramethylammonium hydroxide solution to produce NH(CH3)3OH (trimethylammonium hydroxide) and oxygen atoms. The catalyst adsorbs oxygen atoms. For example, N(CH3)3ClOH reacts with water molecules to produce NH(CH3)3OH and oxygen atoms, while the catalyst adsorbs oxygen atoms generated by the reaction of N(CH3)3ClOH with water molecules, such as chemistry. The reaction formula (2) is shown. then The oxygen atoms adsorbed by the catalyst will further react with NH(CH3)3OH and water molecules, and produce nitrogen and alcohols, as shown by the chemical reaction formula (3).
化學反應式(2)以及化學反應式(3)中的C*表示包括碳元素的觸媒，C*O則表示吸附氧原子的觸媒，而非一氧化碳。由於氧原子本身並不穩定，一般情況下，兩個氧原子會結合成為氧氣(O2)以形成穩定的八隅體結構。本發明則是利用觸媒來吸附氧原子，以避免兩個氧原子結合成為氧氣，如化學反應式(2)所示。之後觸媒所吸附的氧原子可進一步與NH(CH3)3OH以及水分子反應產生氮氣以及醇類，如化學反應式(3)所示。 Chemical Reaction Formula (2) and Chemical Reaction Formula (3) C* represents a catalyst including carbon, and C*O represents a catalyst that adsorbs oxygen atoms, rather than carbon monoxide. Since the oxygen atoms themselves are not stable, in general, the two oxygen atoms combine to form oxygen (O2) to form a stable octahedral structure. In the present invention, a catalyst is used to adsorb oxygen atoms to prevent two oxygen atoms from being combined into oxygen, as shown by the chemical reaction formula (2). The oxygen atoms adsorbed by the catalyst can be further reacted with NH(CH3)3OH and water molecules to produce nitrogen gas and alcohols, as shown in the chemical reaction formula (3).
雖然化學反應式(2)及(3)是以包括碳元素的觸媒為例，但這並非本發明權利範圍的限制，在本發明其他實施例中，只要如前所述，符合具導電性且不會與四甲基氫氧化銨溶液與氧化劑反應後產生的氧原子產生化學反應的條件，即可作為本發明所使用的觸媒。 Although the chemical reaction formulas (2) and (3) are exemplified by a catalyst including carbon, this is not a limitation of the scope of the present invention, and in other embodiments of the present invention, as long as it is as described above, it is in conformity with conductivity. The catalyst which does not chemically react with the oxygen atom generated after the reaction of the tetramethylammonium hydroxide solution and the oxidizing agent can be used as the catalyst used in the present invention.
若不使用觸媒，則結合成為氧氣的氧原子將不會參與化學反應式(3)所述反應，換句話說，化學反應式(3)所述的反應將不會發生。請參考下列不使用觸媒的化學反應式：2N(CH3)3ClOH+2H2O → 2NH(CH3)3OH+2HCl+O2….……(4) If a catalyst is not used, the oxygen atom bonded to oxygen will not participate in the reaction of the chemical reaction formula (3), in other words, the reaction described in the chemical reaction formula (3) will not occur. Please refer to the following chemical reaction formula without using catalyst: 2N(CH3)3ClOH+2H2O → 2NH(CH3)3OH+2HCl+O2..........(4)
NH(CH3)3OH+HOCl → NH(CH3)2ClOH+CH3OH….……(5) NH(CH3)3OH+HOCl → NH(CH3)2ClOH+CH3OH..........(5)
2NH(CH3)2ClOH+2H2O → 2NH2(CH3)2OH+2HCl+O2….……(6) 2NH(CH3)2ClOH+2H2O → 2NH2(CH3)2OH+2HCl+O2..........(6)
NH2(CH3)2OH+HOCl → NH2(CH3)ClOH+CH3OH….……(7) NH2(CH3)2OH+HOCl → NH2(CH3)ClOH+CH3OH...(7)
2NH2(CH3)ClOH+2H2O → 2NH3(CH3)OH+2HCl+O2….……(8) 2NH2(CH3)ClOH+2H2O → 2NH3(CH3)OH+2HCl+O2...(8)
為方便後續說明，在此將上述化學反應式(4)至(8)中的NH(CH3)3OH(三甲基氫氧化銨)、NH2(CH3)2OH(二甲基氫氧化銨) 及NH3(CH3)OH(甲基氫氧化銨)通稱為四甲基氫氧化銨衍生物，而化學反應式(4)至(8)中的N(CH3)3ClOH(一氯三甲基氫氧化銨)、NH(CH3)2ClOH(一氯二甲基氫氧化銨)及NH2(CH3)ClOH(一氯甲基氫氧化銨)通稱為四甲基氫氧化銨氯化物。 For the convenience of the following description, NH(CH3)3OH (trimethylammonium hydroxide) and NH2(CH3)2OH (dimethylammonium hydroxide) in the above chemical reaction formulas (4) to (8) are used herein. And NH3(CH3)OH (methylammonium hydroxide) is commonly known as tetramethylammonium hydroxide derivative, and N(CH3)3ClOH (monochlorotrimethylhydroxide) in the chemical reaction formulas (4) to (8) Ammonium), NH(CH3)2ClOH (monochlorodimethylammonium hydroxide) and NH2(CH3)ClOH (monochloromethylammonium hydroxide) are commonly referred to as tetramethylammonium hydroxide chloride.
四甲基氫氧化銨衍生物與氧化劑反應會產生四甲基氫氧化銨氯化物，如化學反應式(5)、(7)所示，而四甲基氫氧化銨氯化物與水作用後又會產生四甲基氫氧化銨衍生物以及氧氣，如化學反應式(4)、(6)、(8)所示。換句話說，若不使用本發明所述的觸媒，四甲基氫氧化銨溶液則無法被分解轉換為氮氣及醇類。 The reaction of the tetramethylammonium hydroxide derivative with the oxidant produces tetramethylammonium hydroxide chloride, as shown by the chemical reaction formulas (5) and (7), and the tetramethylammonium hydroxide chloride reacts with water. A tetramethylammonium hydroxide derivative and oxygen are produced as shown in the chemical reaction formulas (4), (6), and (8). In other words, the tetramethylammonium hydroxide solution cannot be decomposed into nitrogen and alcohol without using the catalyst of the present invention.
在本發明一實施例中，氧化劑的用量為所須莫爾當量數的1至1.2倍。本發明所述之當量數，是指平衡前述化學反應式(1)、(2)、(3)所須使用的氧化劑莫耳數。雖然化學反應式(1)中是以次氯酸作為氧化劑，但次氯酸僅為本發明其中一實施例，並非本發明權利範圍的限制，在本發明其他實施例中，氧化劑可以是次氯酸鹽或是其他包括次氯酸根的液體，例如次氯酸鈉、次氯酸鈣、次氯酸鈉溶液或次氯酸鈣溶液。 In an embodiment of the invention, the oxidizing agent is used in an amount of from 1 to 1.2 times the number of moles required. The equivalent number in the present invention means the number of moles of the oxidizing agent to be used for balancing the chemical reaction formulas (1), (2), and (3). Although hypochlorous acid is used as the oxidizing agent in the chemical reaction formula (1), hypochlorous acid is only one embodiment of the present invention and is not a limitation of the scope of the present invention. In other embodiments of the present invention, the oxidizing agent may be hypochlorite. An acid salt or other liquid including hypochlorite, such as sodium hypochlorite, calcium hypochlorite, sodium hypochlorite solution or calcium hypochlorite solution.
在本發明一實施例中，觸媒、N(CH3)3ClOH以及四甲基氫氧化銨溶液中的水分子混合或接觸後，會產生NH(CH3)3OH(三甲基氫氧化銨)以及鹽酸，如化學反應式(2)所示。 In one embodiment of the present invention, NH(CH3)3OH (trimethylammonium hydroxide) and hydrochloric acid are produced after mixing or contacting water molecules in a catalyst, N(CH3)3ClOH, and tetramethylammonium hydroxide solution. , as shown in the chemical reaction formula (2).
由於本發明所述的四甲基氫氧化銨溶液的分解方法在偏酸的環境下進行，會產生毒性較強的Cl2及/或Cl3，為此在本發明一實施例中，可加入一鹼，例如氫氧化納，使鹼與鹽酸酸鹼中和。在本發明一較佳實施例中，可使用氫氧化鈉將酸鹼值調整至大於PH7，來避免Cl2及/或Cl3的產生。 Since the decomposition method of the tetramethylammonium hydroxide solution of the present invention is carried out under a biased acid environment, a highly toxic Cl2 and/or Cl3 may be produced. For this purpose, in one embodiment of the present invention, a base may be added. For example, sodium hydroxide is used to neutralize the base with hydrochloric acid. In a preferred embodiment of the invention, sodium hydroxide can be used to adjust the pH to greater than pH 7 to avoid the production of Cl2 and/or Cl3.
透過本發明所述的四甲基氫氧化銨溶液的分解方法，可使四甲基氫氧化銨溶液中的四甲基氫氧化銨去除率達到99%以上。以一般半導體製程所產生的四甲基氫氧化銨廢水為例，廢水中的四甲基氫氧化銨濃度約在4000ppm以下，透過本發明所述的四甲基氫氧化銨溶液的分解方法，可將廢水中的四甲基氫氧化銨濃度降至1ppm以下，因此四甲基氫氧化銨的去除率為99.975%以上，請參考下列計算式：
本發明所述的四甲基氫氧化銨溶液的分解方法，可以進一步應用在四甲基氫氧化銨溶液的分解裝置中。 The method for decomposing the tetramethylammonium hydroxide solution of the present invention can be further applied to a decomposition apparatus of a tetramethylammonium hydroxide solution.
請參閱第2圖，為本發明四甲基氫氧化銨溶液的分解裝置一實施例的構造示意圖。如圖所示，四甲基氫氧化銨溶液的分解裝置20包括一混合槽21、至少一傳輸管24以及一觸媒槽22，其中混合槽21透過傳輸管24連接觸媒槽22。 Please refer to FIG. 2, which is a schematic structural view of an embodiment of a decomposition apparatus for a tetramethylammonium hydroxide solution of the present invention. As shown, the decomposition apparatus 20 of the tetramethylammonium hydroxide solution includes a mixing tank 21, at least one transfer tube 24, and a catalyst tank 22, wherein the mixing tank 21 is connected to the catalyst tank 22 through the transfer tube 24.
混合槽21用以混合四甲基氫氧化銨溶液以及氧化劑，其中四甲基氫氧化銨溶液包括四甲基氫氧化銨及水分子，氧化劑包括次氯酸根或次氯酸鹽。四甲基氫氧化銨溶液中的四甲基氫氧化銨與氧化劑在混合槽21中混合，並產生N(CH3)3ClOH(一氯三甲基氫氧化銨)。 The mixing tank 21 is used to mix a tetramethylammonium hydroxide solution including tetramethylammonium hydroxide and water molecules, and an oxidizing agent including hypochlorite or hypochlorite. Tetramethylammonium hydroxide in the tetramethylammonium hydroxide solution is mixed with the oxidizing agent in the mixing tank 21 to produce N(CH3)3ClOH (monochlorotrimethylammonium hydroxide).
觸媒槽22用以容置一觸媒23，並透過傳輸管24由混合槽21接收N(CH3)3ClOH及四甲基氫氧化銨溶液中的水分子，使得水分子與N(CH3)3ClOH反應產生NH(CH3)3OH(一氯三甲基氫氧化銨)及氧原子，且觸媒23吸附水分子與N(CH3)3ClOH反應所產生的氧原子，並使 NH(CH3)3OH、觸媒23所吸附的氧原子以及水分子繼續在觸媒槽22中反應產生氮氣以及醇類。 The catalyst tank 22 is for accommodating a catalyst 23, and receives water molecules in the N(CH3)3ClOH and tetramethylammonium hydroxide solutions from the mixing tank 21 through the transfer tube 24, so that the water molecules and the N(CH3)3ClOH The reaction produces NH(CH3)3OH (monochlorotrimethylammonium hydroxide) and an oxygen atom, and the catalyst 23 adsorbs oxygen atoms generated by the reaction of water molecules with N(CH3)3ClOH, and The NH(CH3)3OH, the oxygen atom adsorbed by the catalyst 23, and the water molecules continue to react in the catalyst tank 22 to generate nitrogen gas and alcohol.
當然在實際應用時，混合槽21內的N(CH3)3ClOH及水分子亦可能會產生反應，並於混合槽21內形成NH(CH3)3OH。為此由混合槽21輸送至觸媒槽22的溶液除了N(CH3)3ClOH及水分子之外，可能還包括氧化劑、NH(CH3)3OH及/或鹽酸等。 Of course, in practical use, N(CH3)3ClOH and water molecules in the mixing tank 21 may also react, and NH(CH3)3OH is formed in the mixing tank 21. For this purpose, the solution transported from the mixing tank 21 to the catalyst tank 22 may include an oxidizing agent, NH(CH3)3OH, and/or hydrochloric acid in addition to N(CH3)3ClOH and water molecules.
如本發明四甲基氫氧化銨溶液的分解方法中所述，觸媒23具有導電性，且不會與四甲基氫氧化銨溶液與氧化劑反應後所產生的氧原子產生化學反應。在本發明一實施例中，觸媒23包括碳元素或活性碳，其中活性碳為本發明一較佳的實施例，活性碳具有較大的表面積，其吸附氧原子的效率及數量皆較佳，因此使用活性碳可提升本發明所述的分解裝置的反應速率。 As described in the decomposition method of the tetramethylammonium hydroxide solution of the present invention, the catalyst 23 has electrical conductivity and does not chemically react with oxygen atoms generated after the reaction of the tetramethylammonium hydroxide solution with the oxidizing agent. In an embodiment of the invention, the catalyst 23 comprises carbon or activated carbon, wherein the activated carbon is a preferred embodiment of the invention, the activated carbon has a large surface area, and the efficiency and quantity of adsorbing oxygen atoms are better. Thus, the use of activated carbon can increase the reaction rate of the decomposition apparatus of the present invention.
此外，如本發明四甲基氫氧化銨溶液的分解方法中所述，本發明所述的氧化劑，可以是次氯酸鹽或是其他包括次氯酸根的液體，例如次氯酸鈉、次氯酸鈣、氯酸鈉溶液或次氯酸鈣溶液。 Further, as described in the decomposition method of the tetramethylammonium hydroxide solution of the present invention, the oxidizing agent of the present invention may be hypochlorite or other liquid including hypochlorite, such as sodium hypochlorite or calcium hypochlorite. Sodium chlorate solution or calcium hypochlorite solution.
在本發明一實施例中，混合槽21可包括一輸入端211，用以輸入四甲基氫氧化銨溶液以及氧化劑。 In an embodiment of the invention, the mixing tank 21 can include an input 211 for inputting a solution of tetramethylammonium hydroxide and an oxidizing agent.
在本發明一實施例中，N(CH3)3ClOH與水分子反應會產生NH(CH3)3OH及鹽酸。如本發明四甲基氫氧化銨溶液的分解方法中所述，四甲基氫氧化銨溶液的分解反應在偏酸的環境下進行，會產生毒性較強的Cl2及/或Cl3。為此在本發明一實施例中，可在混合槽21及/或觸媒槽22中加入一鹼，例如透過混合槽21的輸入端211將鹼加入混合槽21，或觸媒槽22可進一步包括一輸入管221，並透過觸媒槽22的輸入管221將鹼加入觸媒槽22，使鹼 與鹽酸酸鹼中和。在本發明一較佳實施例中，可在混合槽21或觸媒槽22中加入氫氧化鈉，將混合槽21及/或觸媒槽22中的酸鹼值調整為大於PH7，來避免Cl2及/或Cl3的產生。 In one embodiment of the invention, N(CH3)3ClOH reacts with water molecules to produce NH(CH3)3OH and hydrochloric acid. As described in the decomposition method of the tetramethylammonium hydroxide solution of the present invention, the decomposition reaction of the tetramethylammonium hydroxide solution is carried out under a biased acid environment, and a highly toxic Cl2 and/or Cl3 is produced. To this end, in an embodiment of the present invention, a base may be added to the mixing tank 21 and/or the catalyst tank 22, for example, the base may be added to the mixing tank 21 through the input end 211 of the mixing tank 21, or the catalyst tank 22 may further An input pipe 221 is included, and an alkali is added to the catalyst tank 22 through the input pipe 221 of the catalyst tank 22 to make a base. Neutralize with hydrochloric acid acid base. In a preferred embodiment of the present invention, sodium hydroxide may be added to the mixing tank 21 or the catalyst tank 22 to adjust the pH value of the mixing tank 21 and/or the catalyst tank 22 to be greater than PH7 to avoid Cl2. And / or the production of Cl3.
在本發明一實施例中，傳輸管24可在混合槽21及觸媒槽21之間形成迴路，使得四甲基氫氧化銨溶液、N(CH3)3ClOH、NH(CH3)3OH或氧化劑經由傳輸管在混合槽21以及觸媒槽22之間流動或循環，如此可達到混拌的效果，以增加氮氣及醇類的產生效率。 In an embodiment of the invention, the transfer tube 24 can form a loop between the mixing tank 21 and the catalyst tank 21, such that the tetramethylammonium hydroxide solution, N(CH3)3ClOH, NH(CH3)3OH or the oxidant is transported. The tube flows or circulates between the mixing tank 21 and the catalyst tank 22, so that the effect of mixing can be achieved to increase the production efficiency of nitrogen and alcohol.
當然在本發明四甲基氫氧化銨溶液的分解裝置的另一實施例中，亦可不包括觸媒槽22及傳輸管24。混合槽21亦可用以容置觸媒23，並直接使用混合槽21使四甲基氫氧化銨溶液、氧化劑及觸媒23混合或接觸，例如透過一攪拌器(未顯示)使四甲基氫氧化銨溶液、氧化劑及觸媒23混合或接觸，以產生氮氣及醇類。 Of course, in another embodiment of the decomposition apparatus of the tetramethylammonium hydroxide solution of the present invention, the catalyst tank 22 and the transfer tube 24 may not be included. The mixing tank 21 can also be used to accommodate the catalyst 23, and directly mix or contact the tetramethylammonium hydroxide solution, the oxidizing agent and the catalyst 23 by using the mixing tank 21, for example, through a stirrer (not shown) to make tetramethylhydrogen. The ammonium oxide solution, the oxidizing agent, and the catalyst 23 are mixed or contacted to produce nitrogen gas and alcohol.
說明書中所描述之也許、必須及變化等字眼並非本發明之限制。說明書所使用的專業術語主要用以進行特定實施例的描述，並不為本發明的限制。說明書所使用的單數量詞(如一個及該個)亦可為複數個，除非在說明書的內容有明確的說明。例如說明書所提及之一個裝置可包括有兩個或兩個以上之裝置的結合，而說明書所提之一物質則可包括有多種物質的混合。 The words "may," and "changes" as described in the specification are not limitations of the invention. The technical terms used in the specification are mainly for the description of specific embodiments and are not intended to be limiting. The single quantifiers (such as one and the one) used in the specification may also be plural, unless explicitly stated in the contents of the specification. For example, a device referred to in the specification may include a combination of two or more devices, and one of the materials mentioned in the specification may include a mixture of a plurality of substances.
以上所述者，僅為本發明之較佳實施例而已，並非用來限定本發明實施之範圍，即凡依本發明申請專利範圍所述之形狀、構造、特徵及精神所為之均等變化與修飾，均應包括於本發明之申請專利範圍內。 The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, that is, the variations, modifications, and modifications of the shapes, structures, features, and spirits described in the claims of the present invention. All should be included in the scope of the patent application of the present invention.
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| CN1463253A (en) * | 2001-05-21 | 2003-12-24 | 三菱电机株式会社 | Process and appts. for treating nitrogen compound contg. water |
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| TW204328B (en) * | 1990-12-13 | 1993-04-21 | Mitsubishi Gas Chemical Co | |
| CN1463253A (en) * | 2001-05-21 | 2003-12-24 | 三菱电机株式会社 | Process and appts. for treating nitrogen compound contg. water |
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