TW201210942A - Method for converting fluoride ion in waste liquid into hydrofluoric acid with high purity and high concentration - Google Patents
Method for converting fluoride ion in waste liquid into hydrofluoric acid with high purity and high concentration Download PDFInfo
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201210942 六、發明說明： 【發明所屬之技術領域】 本發明係有關於一種廢液處理方法，尤其是一種含無 機氟化物廢液的處理方法，藉此方法可將廢液中的氟離子 轉化為高純度高濃度的氫氟酸。 【先前技術】 工業廢液中，常含有金屬離子、金屬與氟離子的錯合 物、自由氟離子（F)、氫氟酸（hydrofluoric acid，HF)等化合 • 物，例如金屬酸洗廢液等，一般處理此種廢液的方式，係 先加入如氫氧化鈉（sodium hydroxide，NaOH )等驗類中和 酸性’並使二價與三價金屬形成不溶的氳氧化物 (hydroxides)，將沉澱之氫氧化物以過濾的方式移除後，再 加入鈣離子（Ca2+)使其與氟離子反應形成不溶於水的氟化鈣 (CaF2)，然而，不溶的氫氧化物與氟化鈣均需要花費金錢處 理並妄棄’因此既有之廢液處理方式費用頗高。 【發明内容】 •本發明人有鑑於既有的廢液中之無機氟化物處理方法 會生成不溶的氫氧化物與氟化鈣等固態化合物，因此需要 化費金錢處理並丟棄，經過長時間的研究以及不斷試驗後 ，終於發明出此含無機氟化物廢液處理方法，藉此方法可 將廢液中的氟離子轉化成高純度高濃度的氣氣酸回收 用。 具體而言，本發明之目的在於提供一種能夠將廢液中 的氟離子轉化為高純度高濃度氫氟酸的方法，其包括下列 201210942 步驟： a.在含有無機說化物與金屬 廢液中的自由氟離子轉化成氫氟 離子的廢液中力Π A草酸使 酸而形成含氫氟酸的溶液 ^广使二亥含氫氟酸的溶液經由逆向滲透膜分離 付尚純度高濃度的氫氟酸溶液。 又 其中，將獲得的氫I酸溶液，進一步加 臭氧以移除直中可能iS坍a a a 孔化氫或 ” .g择 逆向滲透膜的草酸’而獲取高純 度冋濃度的氫氟酸溶液。 、·电 〃其中，將含無機氟化物與金屬離子的廢液加 虱離子轉化為氫氟酸而形成含氫氟酸的溶液後，該含 I的冷液中係包括金屬草酸鹽和金屬草酸根錯合物。 其中，該含氫氟酸的溶液在通過逆向滲透膜分離過程 之前係尚包括將含氫氟酸的溶液進行過滤以移除不溶的金 屬草酸鹽。在金屬草酸鹽中’金屬為正—價或正三價時， 其金屬草酸鹽和金屬草酸根錯合物可溶；金屬為正二價時 ’其金屬草酸鹽不溶》 、 其中，所述的金屬離子係選自由下列所述之化合物所 組成之群組：一價的金屬陽離子、氨根離子、二價的金屬 陽離子、三價的金屬及其與氟離子形成之化合物和錯合物 較佳的，金屬離子係選自由下列所述之化合物所組成 之群組：鈉離子（Na+)、鉀離子（K+)、氨根離子（NH/)、亞 鐵離子（Fe2+)、鈷離子（Co2+)、鎳離子（Ni2+)、銅離子（Cu2+) 、鋅離子（Zn2+)、鎘離子（Cf) '汞離子（Hg2+)、鉛離子 201210942 ㈣）、三價的鐵離子（Fe3+)、㈣子 :子形成之化合物、三價的鐵與，離子形成之-=與-氣 =與氧離子形成之化合物和三價的絡與說離子形成: 本發明所提供的將廢液中氟離子轉化為氫氣酸的方法 ，藉由上述技術手段，至少包括以下優點： 卜本發明於廢液中添加草酸，使自由氟離子形成氯款 酸並回收。201210942 VI. Description of the Invention: [Technical Field] The present invention relates to a waste liquid treatment method, and more particularly to a treatment method comprising an inorganic fluoride waste liquid, whereby a fluoride ion in a waste liquid can be converted into High purity and high concentration of hydrofluoric acid. [Prior Art] Industrial waste liquids often contain metal ions, complexes of metal and fluoride ions, free fluoride ions (F), hydrofluoric acid (HF), etc., such as metal pickling waste liquid Etc., the general way of treating such waste liquid is to first add a hydroxide such as sodium hydroxide (NaOH) to neutralize the acidity and make the divalent and trivalent metals insoluble hydroxides. After the precipitated hydroxide is removed by filtration, calcium ions (Ca2+) are added to react with fluoride ions to form water-insoluble calcium fluoride (CaF2). However, both insoluble hydroxide and calcium fluoride are dissolved. It takes money to process and abandon 'so the cost of the existing waste treatment is quite high. SUMMARY OF THE INVENTION The present inventors have in view of the fact that the inorganic fluoride treatment method in the existing waste liquid generates solid compounds such as insoluble hydroxides and calcium fluoride, and therefore needs to be treated and discarded, and after a long period of time. After research and continuous testing, this method of treating inorganic fluoride waste liquid was finally invented, and the method can convert fluorine ions in the waste liquid into high-purity and high-concentration gas-gas acid recovery. Specifically, it is an object of the present invention to provide a method capable of converting fluoride ions in a waste liquid into high-purity, high-concentration hydrofluoric acid, which comprises the following steps 201210942: a. in containing inorganic salts and metal waste liquids The free liquid fluoride is converted into a waste liquid of hydrofluoride ion. A oxalic acid is used to form an acid-containing solution containing hydrofluoric acid. The solution of the hydrofluoric acid in Erhai is separated by a reverse osmosis membrane to treat a high concentration of hydrofluoric acid. Acid solution. In addition, the obtained hydrogen I acid solution is further added with ozone to remove the hydrolyzed acid solution of the high-purity cerium concentration by removing the osmotic acid which may be iS坍aaa or ".g of the reverse osmosis membrane." In the electric sputum, after the waste liquid containing inorganic fluoride and metal ions is converted into hydrofluoric acid to form hydrofluoric acid-containing solution, the I-containing cold liquid includes metal oxalate and metal oxalic acid. Root complex. Among them, the hydrofluoric acid-containing solution includes filtering the hydrofluoric acid-containing solution to remove the insoluble metal oxalate before passing through the reverse osmosis membrane separation process. When the metal is a positive or a valence, the metal oxalate and the metal oxalate complex are soluble; when the metal is a positive divalent, the metal oxalate is insoluble, wherein the metal ion is selected from A group consisting of a compound of the following: a monovalent metal cation, an ammonia ion, a divalent metal cation, a trivalent metal, and a compound and a complex thereof formed with a fluoride ion, preferably a metal ion system Choose the following Group of compounds: sodium ion (Na+), potassium ion (K+), ammonia ion (NH/), ferrous ion (Fe2+), cobalt ion (Co2+), nickel ion (Ni2+), copper ion (Cu2+), zinc ion (Zn2+), cadmium ion (Cf) 'mercury ion (Hg2+), lead ion 201210942 (four)), trivalent iron ion (Fe3+), (four) sub-substrate compound, trivalent iron and , ion formation -= and - gas = compound formed with oxygen ions and trivalent complex and ion formation: the method for converting fluoride ions in the waste liquid into hydrogen acid provided by the present invention, by the above technical means, At least the following advantages are included: The invention adds oxalic acid to the waste liquid, and forms free chlorine ions to form chlorine acid and recovers.
2、先前技術中係將二價的金屬離子形成氫氧化物而丢 棄’但本發明係將二價的金屬形成不溶的草酸鹽過遽收集 後可作其他利用。 3、 本發明係在通過逆向滲透膜分離過程後所獲取之含 氫氟酸的溶液中加人過氧化氫或臭氧用以氧化可能通過逆 向滲透膜的草酸而成為二氧化碳’令回收的氫款酸溶液令 沒有草酸，而獲得高純度高濃度的氫氟酸。 4、 本發明於添加草酸後，草酸可轉化自由氟離子為氫 氟酸，可使二價的金屬陽離子形成不溶的草酸鹽、草酸根 與三價金屬的親合力冑大於敦離因而形&金屬草酸根 錯合物而釋放出本來與金屬結合的氟離子進而使氟離子成 為氫氟酸並回收，此工藝可適用於含有無機氟化物及不同 種類之金屬的廢液。 【實施方式】 為能詳細暸解本發明的技術特徵及實用功效並可依 照說明書的内容來實施，詳細說明如後。 201210942 請參照圖1所示，本發明係相關於一種將廢液中氟離 子轉化成高純度高濃度氫氟酸的方法，其中含無機氣化物 的廢液首先藉由過濾除去雜質，因為草酸（〇xalic acid， H2C2〇4)的酸性比氫氟酸（hydrofluoric acid，HF)強，所以接 著在廢液中加入草酸可使廢液中的自由氟離子轉化為氫氟 酸而形成含氫氟酸的溶液，此時含氫氟酸的溶液中若含有 不溶的草酸鹽沉澱則進一步進行過濾，藉此將固態的草酸 鹽移除而獲得一經過濾後含氫氟酸的溶液，然後將此溶液 • 通過逆向滲透膜分離過程後，使溶液中的氫氟酸和部分的 水通過逆向滲透膜，而離子和大部份的水則不能通過。在 通過的氫氟酸溶液中，再加入過氧化氫（h2〇2)或臭氧 使可能通過逆向滲透膜的草酸氧化成c〇2,藉此可獲取高 純度咼濃度的氫氟^酸溶液回收再利用。 本發明所指的逆向滲透膜即R0(Reverse 〇sm〇sis)膜， 而本發明所述之逆向滲透膜分離過程為現有技術中已知的 過程’例如文獻 Ashish Kulkarni，Debabrata Mukherjee， • Devamita Mukherjee, William N. Gill, Reprocessing hydrofluoric acid etching solutions by reverse osmosis, C/ze;«•五《g. Coww. 1994, Vol. 129, pp_ 53-68 與 Debabrata2. In the prior art, divalent metal ions are formed into hydroxides and discarded. However, in the present invention, divalent metals are formed into insoluble oxalates which are collected and used for other purposes. 3. The present invention is characterized in that hydrogen peroxide or ozone is added to a solution containing hydrofluoric acid obtained after the reverse osmosis membrane separation process to oxidize oxalic acid which may pass through the reverse osmosis membrane to become carbon dioxide. The solution was free of oxalic acid to obtain a high purity and high concentration of hydrofluoric acid. 4. After adding oxalic acid according to the present invention, oxalic acid can convert free fluoride ions into hydrofluoric acid, and the divalent metal cation can form insoluble oxalate, and the affinity of oxalate and trivalent metal is greater than that of The metal oxalate complex dissolves the fluoride ion originally bound to the metal and further converts the fluoride ion into hydrofluoric acid, and the process can be applied to a waste liquid containing inorganic fluoride and different kinds of metals. [Embodiment] In order to understand the technical features and practical effects of the present invention in detail, and in accordance with the contents of the specification, the detailed description is as follows. 201210942 Please refer to FIG. 1 , which relates to a method for converting fluoride ions in waste liquid into high-purity and high-concentration hydrofluoric acid, wherein the waste liquid containing inorganic gas is first removed by filtration because of oxalic acid ( 〇xalic acid, H2C2〇4) is more acidic than hydrofluoric acid (HF), so adding oxalic acid to the waste liquid can convert free fluoride ions in the waste liquid into hydrofluoric acid to form hydrofluoric acid. a solution in which the hydrofluoric acid-containing solution is further filtered if it contains an insoluble oxalate precipitate, thereby removing the solid oxalate to obtain a filtered hydrofluoric acid-containing solution, and then Solution • After the reverse osmosis membrane separation process, the hydrofluoric acid and part of the water in the solution are passed through the reverse osmosis membrane, while the ions and most of the water cannot pass. In the passed hydrofluoric acid solution, hydrogen peroxide (h2〇2) or ozone is further added to oxidize oxalic acid which may pass through the reverse osmosis membrane to c〇2, thereby obtaining a high-purity hydrazine concentration hydrofluoric acid solution recovery. Reuse. The reverse osmosis membrane referred to in the present invention is a R0 (Reverse 〇sm〇sis) membrane, and the reverse osmosis membrane separation process of the present invention is a process known in the prior art', for example, the literature Ashish Kulkarni, Debabrata Mukherjee, • Devamita Mukherjee , William N. Gill, Reprocessing hydrofluoric acid etching solutions by reverse osmosis, C/ze; «•五"g. Coww. 1994, Vol. 129, pp_ 53-68 with Debabrata
Mukherjee, Ashish Kulkarni, William N. Gill, Membrane based system for ultrapure hydrofluoric acid etching solutions, Journal of Membrane Science 109 (1996) 205-217 所提及，其係依靠氫氟酸在壓力下對於逆向滲透膜的獨特 滲透性。因為氫氟酸是弱酸，且體積與水分子相近，因此 可與水通過逆向滲透膜，而所有離子均不能通過。藉由調 6 201210942 =向滲透时離過程中㈣作條件，例如反應器^力 =低和停留的時間等，可獲得高濃度氫氟酸溶液。且體 發明中，於加麼環境下，將含有氯氣酸的溶液 :二裝有逆向滲透膜的反應器中，至少9〇%的氫氣酸和 二的水會通過逆向渗透膜而被回收，其餘大部份的水和 斤=子均不能通過逆向滲透膜而由另―出口送出反應器 ★量未反應的草酸亦可能通過逆向滲透膜，所以使回收 的氫氟酸溶液中經過氧化氫或臭氧的處理，草酸即被氧化 為C:2’因而獲得高純度高濃度的氫氟酸溶液。 田廢液中存在自由氟離子、氫氟酸及帶有一價的金屬 咬子時如鈉離子（Na+)、鉀離子（κ+)及氨根離子（Nh4+)， 請參閱反應式-所示，於廢液中添加草酸後，由於與氮氣 Ζ ¥酸的酸性較強(ki = 5 9χΐ〇_2)，能使自由氟離子 《成氫氟l (ka-3.5xl〇 4),再將含氫氟酸的溶液經過逆向滲 ，膜分離過程’使氫氟酸與其他離子分離，並於回收的氫 氟酸冷液中加入過氧化氫或臭氧，以除去可能也通過逆向 渗透膜的草酸，即可回收高純度，^農度的氫氟酸，請參 閱反應式二及三所示。 F + H2C2〇4 --► HF+HC2O4' 反應式*- H2C2O4 + h2〇2 -► 2C〇2 + 2H20 反應式二 Η2〇2〇4 + 〇3--► 2C02 + H2〇 + Ο [s] 反應式三 7 201210942 此外若廢液中包括帶有兩價的金屬陽離子（以μ，表 不），如亞鐵離子（Fe2+)、鈷離子（c〇2+)、鎳離子（Ni2+) '銅 離子（Cu2+)、鋅離子（Zn2+)、鑛《離子（Cd2+)、汞離子（Hg2+)、 :離子（Pb )等’凊參閱反應式四所示，加人草酸後，金屬 陽離子將形成固態的金屬草酸鹽沉澱’將沉澱的金屬草酸 鹽(M’C2〇4)過濾後即可移除部分或大部分的金屬，再經過 逆向滲透膜分離過程，使溶液中之1^酸和少量的水得以 通過逆向滲透膜，而所有離子和大部份的水則無法通過而 被排出。在通過逆向滲透膜的氫氟酸溶液中加人過氧化氮 或臭氧以除去可能也通過逆向滲透膜的草酸，即可回收高 純度和高濃度的氫氟酸。某些金屬草酸鹽可做其他用途， 例如反應式四中的Μ·為鎳離子時，生成NiC2〇4可用以製造 催化劑’極具有商業價值。Mukherjee, Ashish Kulkarni, William N. Gill, Membrane based system for ultrapure hydrofluoric acid etching solutions, Journal of Membrane Science 109 (1996) 205-217, which relies on the uniqueness of hydrofluoric acid for reverse osmosis membranes under pressure Permeability. Because hydrofluoric acid is a weak acid and has a volume close to that of water molecules, it can pass through the reverse osmosis membrane with water, and all ions cannot pass. A high concentration hydrofluoric acid solution can be obtained by adjusting 6 201210942 = conditions for the infiltration process (4), such as reactor pressure = low and residence time. In the invention, under the environment of adding, the solution containing chlorine acid: two reactors equipped with reverse osmosis membrane, at least 9% hydrogen acid and two water will be recovered through the reverse osmosis membrane, and the rest Most of the water and jin = can not be sent back to the reactor through the reverse osmosis membrane. The amount of unreacted oxalic acid may also pass through the reverse osmosis membrane, so the recovered hydrofluoric acid solution is subjected to hydrogen peroxide or ozone. The treatment of oxalic acid is oxidized to C:2' thus obtaining a high-purity, high-concentration hydrofluoric acid solution. In the waste liquid, there are free fluoride ions, hydrofluoric acid and metal ions with a monovalent such as sodium ion (Na+), potassium ion (κ+) and ammonia ion (Nh4+). Please refer to the reaction formula - After the addition of oxalic acid to the waste liquid, the acidity of the acid is stronger (ki = 5 9 χΐ〇 2) with the nitrogen hydrazine, so that the free fluoride ion can be converted into hydrogen fluoride (ka-3.5xl 〇 4), and then The hydrofluoric acid solution is subjected to reverse osmosis, and the membrane separation process 'separates hydrofluoric acid from other ions, and hydrogen peroxide or ozone is added to the recovered hydrofluoric acid cold liquid to remove oxalic acid which may also pass through the reverse osmosis membrane. High-purity, agricultural-grade hydrofluoric acid can be recovered, see Equations 2 and 3. F + H2C2〇4 --► HF+HC2O4' Reaction formula *- H2C2O4 + h2〇2 -► 2C〇2 + 2H20 Reaction formula 2〇2〇4〇 〇3--► 2C02 + H2〇+ Ο [s ] Reaction formula 3 7 201210942 In addition, if the waste liquid includes a metal cation with a double valence (in μ, not shown), such as ferrous ion (Fe2+), cobalt ion (c〇2+), nickel ion (Ni2+) Copper ion (Cu2+), zinc ion (Zn2+), ore "ion (Cd2+), mercury ion (Hg2+), : ion (Pb), etc." See reaction formula 4, after adding oxalic acid, the metal cation will form a solid The metal oxalate precipitate 'filters the precipitated metal oxalate (M'C2〇4) to remove some or most of the metal, and then reverse osmosis membrane separation process to make the acid in the solution A small amount of water can pass through the reverse osmosis membrane, and all ions and most of the water cannot pass through. High purity and high concentration of hydrofluoric acid can be recovered by adding peroxidic nitrogen or ozone to the hydrofluoric acid solution passing through the reverse osmosis membrane to remove oxalic acid which may also pass through the reverse osmosis membrane. Some metal oxalates can be used for other purposes. For example, when ruthenium in the reaction formula 4 is nickel ion, the formation of NiC2〇4 can be used to manufacture a catalyst, which is extremely commercially valuable.
M’F2 + H2c204 -► M’C2〇4 j + 2HF 反應式四 再者’若廢液中進一步包括帶有三價的金屬（以M，，表 示），例如不鏽鋼的酸洗廢液中有三價的鐵和三價的鉻等， 這些三價的金屬會與氟離子產生鍵結而形成㈣、响3·、 ⑽、FeF〆等錯合物’若不加草酸，錯合物中的氟離子則 無法回收為氫氟酸，請參閱反應式五和六所示，於加入草 酸後，由於草酸根(C2〇，)相較於氟離子而言，能與三價的 鐵或三價的鉻形成更強的鍵結，吨的合成常數——η constant)約為10丨2,而叫⑽4)33·則為1〇2〇,因此能取代氟 離子與金屬產生鍵結’而使錯合物中的氟離子釋出並形成 201210942 氫氟酸，在不鏽鋼的酸洗廢液中，錯合物中的氟離子可達 到全部氟化合物中氟含量的40%。M'F2 + H2c204 -► M'C2〇4 j + 2HF Reaction Formula 4 'If the waste liquid further includes a metal with a trivalent value (expressed as M,), there is a trivalent value in the pickling waste liquid such as stainless steel. Iron and trivalent chromium, etc., these trivalent metals will bond with fluoride ions to form (4), ring 3, (10), FeF〆 and other complexes. If no oxalic acid is added, fluoride ions in the complex It cannot be recovered as hydrofluoric acid. Please refer to the reaction formulas 5 and 6. After adding oxalic acid, oxalate (C2〇,) can be compared with trivalent iron or trivalent chromium. Forming a stronger bond, the synthesis constant of ton - η constant) is about 10 丨 2, and it is called (10) 4) 33 · is 1 〇 2 〇, so it can replace the fluorine ion and the metal to create a bond 'to make a mismatch The fluoride ion in the product is released and forms 201210942 hydrofluoric acid. In the pickling waste liquid of stainless steel, the fluoride ion in the complex can reach 40% of the fluorine content of all fluorine compounds.
M”F3+ 3H2C204 -► [M”(C2〇4)3]·3 + 3H+ + 3HF 反應式五M”F3+ 3H2C204 -► [M”(C2〇4)3]·3 + 3H+ + 3HF Reaction Formula 5
M”F6_3 + 3H2C2〇4 ^ [M”(C2〇4)3r3 + 6HF 反應式六M"F6_3 + 3H2C2〇4 ^ [M"(C2〇4)3r3 + 6HF Reaction Formula 6
加入草gt後，二彳貝金屬的敗化物和錯合物與草酸作用 形成金屬草酸根錯合物和氫氟酸，再經過逆向滲透膜分離 過程，使超過90%的氫氟酸和少量的水通過逆向滲透膜， 而金屬草酸化合物（包括金屬草酸鹽和金屬草酸根錯合物、)及 其他離子和大部份的水則不得通過。 本發明方法中所使用的草 子形成不溶化合物的酸，例如 殿出多種二價和三價的金屬， 氟酸。 酸亦可換成任何可與金屬離 用磷酸來取代草酸，藉此沉 並回收高純度和高濃度的氫After adding grass gt, the ruthenium compound and the complex compound of the second mussel metal react with oxalic acid to form a metal oxalate complex and hydrofluoric acid, and then undergo a reverse osmosis membrane separation process to make more than 90% of hydrofluoric acid and a small amount. Water passes through the reverse osmosis membrane, while metal oxalate compounds (including metal oxalates and metal oxalate complexes) and other ions and most of the water are not allowed to pass. The grass used in the method of the present invention forms an acid of an insoluble compound, for example, a plurality of divalent and trivalent metals, hydrofluoric acid. The acid can also be replaced by any metal-substituted phosphoric acid instead of oxalic acid, thereby sinking and recovering high purity and high concentration hydrogen.
實施例 本發明含無機氟化物廢液 以下利用實施例更具體說明 處理方法。 =將含無機氣化物與金屬離子之廢液過遽後除去灰 :不：二雜質’再加入草酸而形成含氫氟酸的溶液。若 有不溶的草酸鹽則违杆讲敁 -^ ^ „ 濾，使固態的草酸鹽移除而獲取 經過濾之含氫氟酸的溶液； 將經過濾之含氫象酸竹 ，使醅知i 、冷液通過逆向渗透膜分離過程 使虱齓酸和少量的水通 艰幻逆向滲透膜，而所有離子和大 9 201210942 部份的水不得㈣逆向滲透膜； 中加入過氣化氫或臭 酸後而獲取高純度高 在通過逆向滲透臈的氫氟酸溶液 氧除去可能通過逆向滲透膜的微量草 濃度的氫氟酸溶液。 相争乂於先前技術以廢液利用二 丟杳士 1員金屬形成風氧化物而 盆的方式處理，本發明方法將金屬形成金屬草酸鹽可辦 ^可利用性，且利用過氧化氫或臭氧可氧化並除去通過EXAMPLES Inorganic fluoride-containing waste liquid of the present invention The treatment method will be more specifically described below by way of examples. = The waste liquid containing inorganic vapor and metal ions is passed through to remove ash: no: two impurities' is further added with oxalic acid to form a hydrofluoric acid-containing solution. If there is insoluble oxalate, then 违-^ ^ „ filter, remove the solid oxalate to obtain filtered hydrofluoric acid-containing solution; filter the hydrogen-containing acid-like bamboo to make 醅Knowing that the cold liquid passes through the reverse osmosis membrane separation process, the tannic acid and a small amount of water pass through the rigorous reverse osmosis membrane, and all the ions and the water of the 201210942 part are not allowed to reversely permeate the membrane; After the odorous acid, high-purity is obtained in the hydrofluoric acid solution by reverse osmosis, and the hydrofluoric acid solution which can pass the trace grass concentration of the reverse osmosis membrane is removed. The prior art uses the waste liquid to utilize the two gentlemen 1 The metal is formed into a wind oxide and treated in a pot. The method of the present invention can form a metal oxalate to form a metal, and can be oxidized and removed by using hydrogen peroxide or ozone.
' °滲透膜而存在於氫氟酸溶液中的草酸，此外，本發明 於廢液中添加草酸可使三價金屬與氟離子錯合物釋出氟離 進而使釋出的氟離子形成氫氟酸並回收，減少資源的 浪費。 准以上所述者’僅為本發明之較佳實施例而已，當不 月匕以此限定本發明實施之範圍，凡依本發明申請專利範圍 及說明書内容所作之簡單的等效變化與修飾，皆應仍屬本 發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1係本發明之流程圖。 【主要元件符號說明】The oxalic acid present in the hydrofluoric acid solution is permeable to the membrane. In addition, the addition of oxalic acid to the waste liquid of the present invention allows the trivalent metal and the fluoride ion complex to release fluorine and thereby cause the released fluoride ion to form hydrofluoric acid. Acid and recycle, reducing waste of resources. The above description is only a preferred embodiment of the present invention, and the equivalent equivalents and modifications made by the scope of the present invention and the contents of the specification are not limited by the scope of the present invention. All should remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart of the present invention. [Main component symbol description]
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105142763A (en) * | 2013-04-25 | 2015-12-09 | 索尔维公司 | Reverse osmosis for purifying mixtures of hydrofluoric acid and nitric acid |
| US9840667B2 (en) | 2013-04-25 | 2017-12-12 | Solvay Sa | Reverse osmosis for purifying mixtures of hydrofluoric acid and nitric acid |
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