12331581233158
【發明所屬之技術領域】 本發，$有關於一種廢水處理系統與方法，且特別有 j ^種氫氟酸處理系統與方法，係、以階段比率式的氣化 氫處理方式來增快氫說酸處理速度與減少加 【先前技術】 ’、 ^亂化氫（Hydr〇gen nuoride，化學式耵）在常溫常 壓下為氣體’溶於水後為一種強酸，稱為氯氣酸 (anhydrous hydrogen f1uoride - f l uorohydric acid. anhydrous hydrofluoric aci〇 。氫氟酸對去除氧化物 的放果非吊★好，故應用在許多行業中，如半導體業中以氫 氟酸作為清洗劑、玻璃蝕刻業中以氫氟酸作為蝕刻劑、鋼 鐵業中以氫氟酸作為表面除鏽劑、石化業中以氫氟酸作為 催化劑、清潔服務業中以氫氟酸作為污物腐蝕清洗劍戒外 牆清洗劑，甚至在家庭裡所用的除鏽劑中皆含有氡氟酸。 然而氫氟酸強烈的腐蝕性與高脂溶性的特性，使它極易穿 過人體，與體内的鈣、鎂離子結合，侵蝕骨骼與肌肉，立 不只皮膚接觸會有傷害，甚至由呼吸道進入人體也會產生 相當的危險，故含有氫氟酸的廢水皆須經過處理，才不會 造成人體的危害與環境的污染。 目鈾半導體業大部分運用#5鹽沈殿法來處理氫氣酸’ 其中#5鹽可為氫氧化舞（calcium hydroxide，化學式 Ca(0H)2)、硫酸#5 (caiciUIn sulfate，化學式caS〇4)戒 氯化#5 (calcium chloride，化學式CaCl2)等，氫氟酸會 與妈鹽形成氟化飼（calcium fluoride，化學式caF2)沈[Technical field to which the invention belongs] This issue relates to a wastewater treatment system and method, and in particular ^ hydrofluoric acid treatment systems and methods, which use a stepwise ratio gasification hydrogen treatment method to accelerate hydrogen It is said that the acid treatment speed and reduction are added. [Prior technology], "Hydrogen nuoride (chemical formula 耵) is a gas at normal temperature and pressure" and dissolved in water is a strong acid, called anhydrous hydrogen f1uoride. -fl uorohydric acid. anhydrous hydrofluoric aci〇. Hydrofluoric acid is not good for removing oxides. Therefore, it is used in many industries, such as the semiconductor industry with hydrofluoric acid as a cleaning agent, and the glass etching industry with hydrogen. Hydrofluoric acid is used as an etchant, hydrofluoric acid is used as a surface rust remover in the iron and steel industry, hydrofluoric acid is used as a catalyst in the petrochemical industry, and hydrofluoric acid is used as a contaminant in the cleaning service industry to clean the sword ring and exterior wall cleaning agents, and even Sulfuric acid is contained in the rust remover used in homes. However, the strong corrosive and high fat-soluble properties of hydrofluoric acid make it easy to pass through the human body and bind to calcium and magnesium ions in the body. Erosion of bones and muscles will not only cause skin contact damage, but also cause considerable danger even from the respiratory tract into the human body, so the wastewater containing hydrofluoric acid must be treated before it will cause harm to the human body and environmental pollution. Most of the uranium semiconductor industry uses the # 5 salt Shendian method to treat hydrogen acid. The # 5 salt can be calcium hydroxide (chemical formula Ca (0H) 2) and sulfuric acid # 5 (caiciUIn sulfate, chemical formula caS〇4). Quit chlorination # 5 (calcium chloride, chemical formula CaCl2), etc. Hydrofluoric acid will form calcium fluoride (calcium fluoride, chemical formula caF2)
0632-A50067TWF(Nl) ； AU0309009 ； ice.ptd 第 5 頁 1233158 、發明說明（2) 氣’而氟化鈣是一種無毒且安定性高的化合物，故可直接 $埋於衛生掩埋場，而剩下的氫氟酸濃度若小於1 5ppm法 疋排放量以下時，即可進行排放。0632-A50067TWF (Nl); AU0309009; ice.ptd page 5 1233158, description of the invention (2) gas and calcium fluoride is a non-toxic and highly stable compound, so it can be directly buried in the sanitary landfill, and the remaining If the concentration of hydrofluoric acid below is less than 15ppm, the emission can be carried out.
習知的氟化氫處理系統之示意圖如第丨圖所示，包括 一反應槽1 0、一混凝槽2 0、一凝聚槽3 0、一淨化槽4 〇、一 污泥槽50、複數個氟離子濃度計6〇與複數個酸鹼度計7〇。 首先氫氟酸廢液Q進入反應槽10，在氟離子濃度固定的情 形下’ «L化鈣的沈澱速率主要受鈣離子濃度與酸鹼度影 響’故根據氟離子濃度計6〇與酸鹼度計7〇來加入氯化齊c 與氫氧化鈉N，且為使反應完全，所添加的氯化鈣c通常為 過量，而氫氧化鈉N的添加是為使整個廢液環境處於鹼性 條件下’以利氟化鈣的形成；但隨著氟離子濃度越低，反 應時間將越長，故通常會在下一步驟再加一次氯化鈣C， 做氟化氫的兩段式處理。 接下來將反應槽1 〇中經處理過的氫氣酸溶液Q引入混 凝槽2 0中’同樣根據氟離子濃度計6 〇與酸鹼度計7 〇來加入 氯化鈣C與氫氧化鈉N，使氟離子去除地更完全，並加入多 元氧化鋁（Poly Aluminium Chloride，簡稱PAC)P1 作為 混凝劑，使微小顆粒的氟化鈣凝結成較大顆粒的膠羽，以 利於沈澱。 接著將此廢液引入凝聚槽3 〇，加入聚合物凝聚劑p 2使 膠羽沈殿；之後將廢液引入淨化槽4 〇進行過濾，滤出的廢 液經氟離子濃度計6 0量測低於法定排放標準時即可進行排 放，剩下的污泥則進入污泥槽50做掩埋準備。A schematic diagram of a conventional hydrogen fluoride treatment system is shown in FIG. 丨 and includes a reaction tank 10, a coagulation tank 20, a coagulation tank 30, a purification tank 40, a sludge tank 50, and a plurality of fluorine. Ion concentration meter 60 and pH meter 70. First, the hydrofluoric acid waste liquid Q enters the reaction tank 10, and when the fluoride ion concentration is fixed, "« The precipitation rate of calcium chloride is mainly affected by the calcium ion concentration and pH ", so according to the fluoride ion concentration meter 60 and the pH meter 7. Calcium chloride c and sodium hydroxide N are added, and in order to complete the reaction, calcium chloride c is usually added in excess, and the addition of sodium hydroxide N is to make the entire waste liquid environment under alkaline conditions. Promote the formation of calcium fluoride; however, as the fluoride ion concentration is lower, the reaction time will be longer, so calcium chloride C is usually added in the next step for two-stage treatment of hydrogen fluoride. Next, the treated hydrogen acid solution Q in the reaction tank 10 is introduced into the coagulation tank 20 '. Similarly, calcium chloride C and sodium hydroxide N are added according to the fluoride ion concentration meter 60 and the pH meter 70, so that The removal of fluoride ions is more complete, and Poly Aluminium Chloride (PAC) P1 is added as a coagulant to coagulate the fine particles of calcium fluoride into larger particles of plume to facilitate precipitation. Then the waste liquid is introduced into the coagulation tank 30, and the polymer coagulant p 2 is added to make the rubber plume sink. After that, the waste liquid is introduced into the purification tank 40 and filtered, and the filtered waste liquid is measured low by a fluoride ion concentration meter 60. Discharge can be carried out at the legal discharge standard, and the remaining sludge enters the sludge tank 50 for landfill preparation.
1233158 五、發明說明（3) 但利用此 不易，為使整 在呂；且由於要 大量的氯化鈣 效盈，同時污 【發明内容】 有4監於此 統與方法，藉 酸處理速度、 為達上述 法處理氫氟酸廢液 體處理時間縮短， 使低濃度的氟離子 ;如此皆會使加藥 泥量也會增大，也 所形成的膠羽細d 需添加更多量的多 反應更加完全，始 量增加，不但不箱 不符合環保效益。 、沈澱 元氧化 需添加 合成本 4^ · 一 第一部 ’本發明的目的就 由階段比率式的氟 減少加藥量與污泥 目的，本發明提供 剷處理槽，用以處理一第 ^ —酸廢液與一過量之 應槽，用以處理一 形成一第二廢液， 及一反 廢液， 疋提供一種氫氟酉〗 化氳處理方式來；t| 量 ° 一種氫氟酸處理系 一部份氫氟酸廢液 鈣鹽反應，形成一 第一部份氫氣酸廢 以產生一可排放和 達上述 一第一 之鈣鹽 與上述 產生一 目的，本發明提供 部份氫氟酸廢液置 ，形成一第一廢液 第一廢液置於一反 可排放和掩埋之廢 :之上述和其他目 牛出較佳實施例， 一種氫氟酸處理1 於一前處理槽中， ;以及將一第二杳 應槽中，形成/驾 棄物。 的、特徵和優點辦 並配合所附圖式， -處理系 快氫IL 統，包 ’使該 第一廢 液與上 掩埋之 法，包 並添加 t氫氟 二廢 更明顯 作詳細 〇632-A50〇67TWF(Nl) ; AU0309009 ； ice.ptd1233158 V. Description of the invention (3) However, it is not easy to use this for the sake of integrity; and because a large amount of calcium chloride is required to benefit, and at the same time it is contaminated. [Summary of the Invention] There are 4 ways to monitor this system and method. In order to achieve the above-mentioned method to shorten the treatment time of hydrofluoric acid waste liquid, so that the low concentration of fluoride ions; this will increase the amount of dosing mud, and the resulting rubber plume d. The response is more complete, and the initial amount is increased, not only is it not inconsistent with environmental protection benefits. The precipitation element oxidation needs to be added to synthesize this 4 ^. A first 'The purpose of the present invention is to reduce the dosing amount of sludge and the purpose of sludge by the phase ratio of fluorine, the present invention provides a shovel processing tank for processing a first ^ — Acid waste liquid and an excess amount of tanks are used to treat one to form a second waste liquid and an anti-waste liquid, which provides a hydrofluoric acid treatment method; t | amount ° a hydrofluoric acid treatment system A part of the hydrofluoric acid waste liquid reacts with the calcium salt to form a first part of the hydrofluoric acid waste to produce a first calcium salt that can be discharged and achieve the above-mentioned first first and the above-mentioned purpose of production. The present invention provides a part of the hydrofluoric acid waste Liquid placement, forming a first waste liquid The first waste liquid is placed in a waste that can be discharged and buried: the above and other preferred embodiments, a hydrofluoric acid treatment in a pre-treatment tank, And put a second echo in the tank to form / drive waste. The characteristics, advantages and advantages of the solution are as follows: -The treatment system is a fast hydrogen IL system, including the method of making the first waste liquid and the method of landfill, and adding and adding hydrogen fluoride to the waste. A50〇67TWF (Nl); AU0309009; ice.ptd
1233158 五、發明說明（4) ' " " " 第2圖為本發明氫氟酸處理系統圖，包含有一計量槽 1 0 0、一前處理槽1 1 0、一反應槽1 2 0、一凝聚槽1 3 0、一淨 化槽1 4 0、—污泥槽1 5 0以及複數個氟離子濃度計1 6 0與一 個或複數個酸驗度計1 7 Q。 首先將氫氟酸廢液引進上述計量槽1 〇 0中，量得一 Q單 位體積’且藉由氟離子濃度計丨6 〇測得氟離子的濃度，乘 上所里彳于的Q單位體積，即可得知此Q單位體積氫氟酸廢液 所，^全數氯化鈣的量；再將XQ (X為百分比）單位體積 的氫氟酸廢液排入上述前處理槽丨丨〇中，剩餘的（1 _χ )卩 ((1-Χ )為百分比）單位體積的氫氟酸廢液排入上述反 1^120中。其中χ最好為1〇%〜2〇%，在此實施例中，χ為 接著於前處理槽no之15%Q單位體積的氫氟酸廢液中 力:入Q早位體積氫I酸廢液所需之全數氯化鈣C，此過量的 :=會二氫氟酸反應形成氟化鈣顆粒，再將此前處理 槽1 1 0中之廢液排入反應槽J 2 〇中。 ，離：ίί前if槽u°中15%Q單位體積的氫氟酸廢液之 氣離子已與乱化别形成氟化舞顆粒，故於反應槽中，可 將此以形成的氟化鈣顆粒視為一 ’w 離子形成氟化舞於上述廢面夜之/:離子會與過量賴 顆粒，如此不但只要添加_ =化：f顆粒較大的氟化約 且所析出的氟化鈣顆粒也較A 卩可將鼠離子析出， _及後續添加的混凝二疑^凝速率㈣’促使氣 剐興喊聚劑之加藥量減少。另1233158 V. Description of the invention (4) '" " " Figure 2 is a diagram of the hydrofluoric acid treatment system of the present invention, including a metering tank 1 0 0, a pre-processing tank 1 1 0, and a reaction tank 1 2 0 , A condensing tank 1 3 0, a purification tank 1 40,-a sludge tank 1 50 and a plurality of fluoride ion concentration meters 16 0 and one or more acid tester 1 7 Q. First introduce the hydrofluoric acid waste liquid into the above-mentioned measuring tank 100, measure a unit volume of Q 'and measure the fluoride ion concentration with a fluoride ion concentration meter, and multiply it by the unit volume of Q , You can know the Q unit volume of hydrofluoric acid waste liquid, the total amount of calcium chloride; then XQ (X is a percentage) unit volume of hydrofluoric acid waste liquid is discharged into the above pre-treatment tank 丨 丨 〇 , The remaining (1_χ) 卩 ((1-χ) is a percentage) unit volume of the hydrofluoric acid waste liquid is discharged into the above-mentioned reaction 1 ^ 120. Among them, χ is preferably 10% to 20%. In this embodiment, χ is a 15% Q unit volume of hydrofluoric acid waste liquid followed by the pretreatment tank no. Force: enter the early volume of hydrogen I The total amount of calcium chloride C required for the waste liquid, this excess: = will react with dihydrofluoric acid to form calcium fluoride particles, and then the waste liquid in the previous processing tank 110 is discharged into the reaction tank J 2 0. The ion of 15% Q unit volume of the hydrofluoric acid waste liquid in the former if tank u ° has formed fluorinated dance particles with the chaos, so in the reaction tank, you can use this to form calcium fluoride The particles are regarded as a 'w ion formed by the fluorinated ion of the above waste surface /: ions will be with the excessive amount of particles, so as long as _ = chemical: f particles larger fluorination about and the precipitated calcium fluoride particles Compared with A 鼠, rat ions can be precipitated. The coagulation rate and subsequent coagulation rate ㈣ 'promote the reduction of the dosage of Qi Xing Xing Chong. another
0632-A50067TWF(Nl) ； AU0309009 ； ice.ptd 第8頁 1233158 五、發明說明（5) 外，同時於反應槽1 2 0中加入一氫氧化鈉N，使氫氟酸廢液 的氟更容易由氳氟酸的形式解離出來，增加氟離子與转離 子的反應速率。此外，再添加多元氯化銘（P〇 1 y Aluminium Chloride，簡稱PAC ) P1 於反應槽120 中，作為 一混凝劑，使氟化鈣形成更大膠羽狀的顆粒，以利沈澱。 之後，將反應槽1 2 0中全部的廢液排入凝聚槽1 3 0中。 在此凝聚槽1 3 0中加入聚合物P2作為一凝聚劑，該聚 合物P2可為％離子型聚丙稀酿胺（anionic polyacrylamide)、陰離子型聚丙烯醯胺二甲基二稀氯化 銨（cationic poly dimethyl dially ammonium chloride)或非離子型聚丙烯醯胺（n〇ni〇nic polyacrylamide )，使膠羽狀的氟化鈣沈澱，再將此廢液 排入上述淨化槽1 4 0中。 將淨化槽140中的廢液進行過濾，其中所產生的污泥 排入污泥槽1 5 0中，經壓縮等處理過後進行掩埋，而剩下 的廢液經氟離子濃度計丨60量測其就離子濃度以低於法定 排放^準1 5 p p in時即可進行排放。 經實際運轉後發現，纟發明之氯氣酸 氟酸的處理時間快兩倍以上，氣系^ Ί便A ,Λ0/夕—〆t 乳化朽的加樂量可減少20% 〜5(U丄多疋氣化鋁與聚合物的加藥量也可減少ι〇%〜 2 0 % ’污泥量也減少了 ，且只雲一 έ备 ^ 、、且氣化雀弓加筚機、，卜h羽 知方式少了 一台加藥機。 ，力桌機比白 並非用以限 雖然本發明已揭露較佳實施例如上，然其 0632-A50067TWF(Nl) ； AU0309009 ； ice.ptd 第9頁 1233158 五、發明說明（6) 定本發明，任何熟習此技藝者，在不脫離本發明之精神和 範圍内，當可作些許之更動與潤飾，因此本發明之保護範 圍當視後附之申請專利範圍所界定者為準。0632-A50067TWF (Nl); AU0309009; ice.ptd Page 8 1233158 V. Description of the invention (5) In addition, at the same time, add sodium monohydroxide N to the reaction tank 12 to make the fluorine of the hydrofluoric acid waste liquid easier. Dissociated from the form of fluorenic acid, increasing the reaction rate of fluoride ion and transion. In addition, a polychlorinated polychloride (P0 1 y Aluminium Chloride, PAC for short) P1 is added to the reaction tank 120 as a coagulant to make calcium fluoride into larger rubber plume-shaped particles to facilitate precipitation. After that, all the waste liquid in the reaction tank 120 was discharged into the coagulation tank 130. A polymer P2 is added to the coagulation tank 130 as a coagulant, and the polymer P2 may be an anionic polyacrylamide, an anionic polypropylene ammonium dimethyl diammonium chloride ( cationic poly dimethyl dially ammonium chloride) or non-ionic polyacrylamide to precipitate gel-like calcium fluoride, and then discharge this waste liquid into the aforementioned purification tank 140. The waste liquid in the purification tank 140 is filtered, and the generated sludge is discharged into the sludge tank 150, which is buried after being treated by compression and the like, and the remaining waste liquid is measured by a fluoride ion concentration meter. 60 It can be discharged when the ion concentration is lower than the legal emission standard of 15 pp in. After actual operation, it was found that the treatment time of the chloro-acid fluoric acid of the 纟 invention was more than twice as fast, and the gas system ^ Ί 便 A, Λ0 / 夕 —〆t The amount of emulsification can be reduced by 20% ~ 5 (U 丄 more量 The dosage of gasified aluminum and polymer can also be reduced by ι0% ~ 20%. 'The amount of sludge has also been reduced, and only one cloud is prepared. There is one less medicating machine in Yuzhi method. The force table machine is not limited to white. Although the preferred embodiment has been disclosed above, its 0632-A50067TWF (Nl); AU0309009; ice.ptd Page 9 1233158 V. Description of the invention (6) Defining the present invention. Any person skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be regarded as the scope of the attached patent. The ones defined shall prevail.
0632-A50067TWF(Nl) ； AU0309009 ； ice.ptd 第10頁 1233158 圖式簡單說明 第1圖為一示意圖，用以說明習知氫氟酸處理系統。 第2圖為一示意圖，用以說明本發明實施例氫氟酸處 理系統。 符號說明j 10 、 120 /反應槽； 2 0〜混凝槽； 3 0、1 3 0〜凝聚槽； 4 0、1 4 0〜淨化槽； 5 0、1 5 0〜污泥槽； 6 0、1 6 0〜氟離子濃度計 7 0、1 7 0〜酸驗度計； I 0 0〜計量槽； II 0〜前處理槽； C〜氯化转； N〜氫氧化納； P1〜多元氧化鋁； P2〜聚合物； Q〜進液量； X〜進液比率。0632-A50067TWF (Nl); AU0309009; ice.ptd Page 10 1233158 Brief Description of Drawings Figure 1 is a schematic diagram for explaining a conventional hydrofluoric acid treatment system. Fig. 2 is a schematic diagram for explaining a hydrofluoric acid processing system according to an embodiment of the present invention. Explanation of symbols: j 10, 120 / reaction tank; 20 to coagulation tank; 30, 130 to coalescence tank; 40, 140 to purification tank; 50, 150 to sludge tank; 60 , 16 0 ~ fluoride ion concentration meter 70, 17 0 ~ acid tester; I 0 0 ~ metering tank; II 0 ~ pretreatment tank; C ~ chlorination conversion; N ~ sodium hydroxide; P1 ~ multivariate Alumina; P2 ~ polymer; Q ~ fluid amount; X ~ fluid ratio.
0632-A50067TWF(N1) ： AU0309009 ； ice.ptd 第11頁0632-A50067TWF (N1): AU0309009; ice.ptd page 11