TW200815625A

TW200815625A - Method and system for recycling and recovering ITO etching waste solution

Info

Publication number: TW200815625A
Application number: TW95136050A
Authority: TW
Inventors: Chin-Hsiung Chang; Yi-Jun Lin; Yao-Jung Fang
Original assignee: San Fu Chemical Co Ltd
Priority date: 2006-09-28
Filing date: 2006-09-28
Publication date: 2008-04-01

Abstract

Disclosed are a method and a system for recycling and recovering ITO (indium tin oxide) etching waste solution. In addition to recycling ITO etching waste solution, the indium and tin also can be recycled with high selectivity. According to this method, waste solution after ITO etching is collected where the waste solution contains oxalate ions. Next, at least two metal ion removal steps are performed. During the first removal step, some of the oxalate ions are exchanged by anion exchange resin, then indium and tin ions in the waste solution are complexed by the exchanged oxalate ions. During the second removal step, most of the other metal ions excluding indium and tin ions are removed to form a recovered solution. Lastly, the concentration of the oxalic acid in the recovered solution is adjusted between 1 wt% and 20 wt% for reusing in the etching of ITO.

Description

200815625 九、發明說明：【發明所屬之技術領域】200815625 IX. Description of the invention: [Technical field to which the invention belongs]

'W 本發明係有關於氧化錫銦蝕刻廢液之回收再利用技術，特別係有關於一種具高選擇性回收銦（Indium)和錫 (Tin)之氧化錫姻触刻廢液之回收再利用方法。【先前技術】在液晶面板與其它電子產業中，使用具有透明線路圖案 • 之玻璃基板是相當重要的零組件，而氧化錫銦（Indium Tin Oxide，ITO)是目前普遍使用的透明導電材料。在經過適當的餘刻處理’以構成所需要的透明線路圖案。目前一種已知常用於蝕刻氧化錫銦之蝕刻液係為約在 3.4%或其它濃度之草酸（oxalic acid)溶液。在經過一段姓刻時間之後，草酸溶液内含大量金屬離子，經分析主要是銦 (In)、錫（Sn)、錢（Cd)、鈉（Na)、鋁（A1)、鉀（K)、鐵（Fe)、錄 (Sr)、鈣（Ca)等金屬離子，這些無法再使用的蝕刻廢液造成 •了環境保護的問題。我國專利公開公報編號第200613582號「酸性餘刻液再生方法及酸性蝕刻液再生裝置」提出一種草酸餘刻廢液之回收再利用方法，便是在一過濾器中以奈米過濾膜 (NanoHltration membrane)對廢液分流處理，調整奈米過瀘、器之過濾流量與迴流量比，將草酸廢液中可過濾為較低金屬離子濃度的過濾液混入新鮮餘刻液，以達回收使用，但這種無調整的混掺方式會影響新鮮餘刻液之草酸濃度。另一方面，迴流較高金屬離子濃度之草酸廢液因混合多項雜質與多種 5 200815625 金屬離子’而且最終回收之金屬離子也僅能下降至ppm等級的濃度’顯然無法達到高效率之回收再利用率，必須與新鮮蝕刻液混掺利用。此外，在草酸蝕刻廢液中，銦離子具有高度經濟價值，若直接排放不但會對環境造成破壞，也是不符產業利用性。【發明内容】本發明之主要目的係在於提供一種氧化錫銦敍刻廢液之回收再利用方法與系統，可以對蝕刻廢液達到高百分比之回收再利用率，大幅降低廢液排放問題，並高選擇性回收銦，深具產業利用性。本發明之次一目的係在於提供一種氧化錫銦蝕刻廢液之回收再利用方法與系統，有進一步將回收的草酸螯a物以灰化或電解提煉⑺winning)得到以上的铜锡成分。本發明的目的及解決其技術問題是採用以下技術方案來實現的。本發明揭示一種氧化錫銦蝕刻廢液之回收再利用方法與系統，該方法中，收集已蝕刻氧化錫銦之廢液，其巾該廢液中係包含有草酸根離子。進行第一次去離子步驟，其係利用離子交換方式，先讀離子型交換樹脂吸附草酸根離子，再以草酸根離子螯合銦離子（In ion)、錫離子（Sn iGii)和其他陰離子型態之含金屬離子。進行第二次去離子步驟’用以去除該廢液中非銦、錫金屬離子，而成為更新液it行- /辰度調配步驟，以使該更新液之草酸之濃度調配在lwt%至20wt%之間。 6 200815625 本發明的目的及解決其技術問題還可採用以下技術措施進一步實現。在前述的回收再利用方法中，另包含有一高溫灰化步驟’其係燃燒由上述第一次去離子步驟取得之草酸螯合物，所得到之灰分係具有高於50wt%的銦錫成分，以回收銦錫金屬。在前述的回收再利用方法中，在上述第二次去離子步驟中，被去除之非銦錫金屬離子係至少包含有鈣離子（Ca ion) 與锶離子（Sr ion)。在前述的回收再利用方法中，上述第二次去離子步驟係包含陽離子型交換樹脂之離子交換。在前述的回收再利用方法中，上述第二次去離子步驟係包含精密過濾（microfiltration)。在前述的回收再利用方法中，在濃度調配步驟中，以加入純水或草酸液方式，以使該更新液之草酸之濃度調配在 2.0wt%至 6.8wt%之間。在前述的回收再利用方法中，另包含有一過濾步驟，其係過濾該更新液之懸浮物。在前述的回收再利用方法中，另包含有一電解提煉 (electrowinning)之步驟，以回收銦。【實施方式】在本發明之一具體實施例中，第1圖係為一種氧化鍚銦蝕刻廢液之回收再利用方法之流程圖。第2圖係為該氧化錫銦蝕刻廢液之回收再利用系統之设備示意 7 200815625 圖如第1圖所示，束發明之氣化錫銦蝕刻廢液之回收再則用方法主要包含有「收集廢液」之步驟1 1、「第一次去離子」步驟12、「第二次去離子」步驟13、「過'W This invention relates to the recycling and recycling technology of indium tin oxide etching waste liquid, in particular to the recycling and recycling of a tin oxide ingot waste liquid with high selective recovery of indium (Indium) and tin (Tin). method. [Prior Art] In the liquid crystal panel and other electronic industries, the use of a glass substrate having a transparent wiring pattern is a very important component, and Indium Tin Oxide (ITO) is a commonly used transparent conductive material. After appropriate appropriate processing, to form the desired transparent line pattern. Currently, an etching solution known to be commonly used for etching indium tin oxide is an oxalic acid solution of about 3.4% or other concentration. After a period of time, the oxalic acid solution contains a large amount of metal ions, and the analysis is mainly indium (In), tin (Sn), money (Cd), sodium (Na), aluminum (A1), potassium (K), Metal ions such as iron (Fe), recorded (Sr), and calcium (Ca), which are etched waste liquids that cannot be reused, pose environmental protection problems. Chinese Patent Publication No. 200613582 "Acid Residue Regeneration Method and Acid Etching Solution Regeneration Apparatus" proposes a method for recycling and recycling oxalic acid waste liquid, which is a nanofiltration membrane in a filter (NanoHltration membrane) The waste liquid is treated by splitting, adjusting the filtration flow rate and the reflux flow ratio of the nano-passing device, and filtering the filtrate which can be filtered into a lower metal ion concentration in the oxalic acid waste liquid into the fresh residual liquid for recycling, but This unadjusted blending method affects the oxalic acid concentration of the fresh residual solution. On the other hand, the oxalic acid waste liquid with a higher metal ion concentration is mixed with a plurality of impurities and a variety of 5 200815625 metal ions 'and the final recovered metal ions can only be reduced to the ppm level concentration' obviously cannot achieve high efficiency recycling. The rate must be mixed with fresh etching solution. In addition, in the oxalic acid etching waste liquid, indium ions have high economic value, and direct discharge not only causes damage to the environment, but also does not conform to industrial utilization. SUMMARY OF THE INVENTION The main object of the present invention is to provide a method and a system for recycling and recycling a tin oxide indium etched waste liquid, which can achieve a high percentage recovery and utilization rate of the etching waste liquid, and greatly reduce the waste liquid discharge problem, and Highly selective recovery of indium, which is highly industrially useful. A second object of the present invention is to provide a method and system for recycling and recycling a tin oxide indium etching waste liquid, which further obtains the above copper tin component by ashing or electrolytically refining (7) winning. The object of the present invention and solving the technical problems thereof are achieved by the following technical solutions. The invention discloses a method and a system for recycling and recycling an indium tin oxide etching waste liquid. In the method, a waste liquid of indium tin oxide is collected, and the waste liquid contains oxalate ions. The first deionization step is carried out by ion exchange, first reading the ion exchange resin to adsorb oxalate ions, and then chelating indium ions, tin ions (Sn iGii) and other anionic species with oxalate ions. The state contains metal ions. Performing a second deionization step 'to remove the non-indium and tin metal ions in the waste liquid, and to become a refreshing liquid-to-time adjustment step, so that the concentration of the oxalic acid of the refreshing liquid is adjusted at 1 wt% to 20 wt. %between. 6 200815625 The object of the present invention and solving the technical problems thereof can be further realized by the following technical measures. In the foregoing recycling method, the method further comprises a high-temperature ashing step of burning the oxalic acid chelate obtained by the first deionization step, and the obtained ash system has an indium tin component of more than 50% by weight. To recover indium tin metal. In the above-described recycling method, in the second deionization step, the non-indium tin metal ions removed include at least calcium ions and strontium ions. In the above recycling method, the second deionization step comprises ion exchange of a cationic exchange resin. In the foregoing recycling method, the second deionization step comprises microfiltration. In the above-mentioned recycling method, in the concentration-adjusting step, pure water or oxalic acid is added to adjust the concentration of the oxalic acid of the refreshing liquid between 2.0 wt% and 6.8 wt%. In the foregoing recycling method, there is further included a filtration step of filtering the suspension of the renewal liquid. In the foregoing recycling method, an electrowinning step is further included to recover indium. [Embodiment] In one embodiment of the present invention, FIG. 1 is a flow chart of a method for recycling and recycling a bismuth oxide indium etching waste liquid. Fig. 2 is a schematic diagram of the apparatus for recycling and recycling the indium tin oxide etching waste liquid. 200815625 As shown in Fig. 1, the recycling method of the vaporized tin indium etching waste liquid of the invention mainly includes Step 1 of "Collecting Waste Liquid" 1. "First Deionization" Step 12, "Second Deionization" Step 13, "Over

慮」步驟14及「濃度調配」之步H 15。在第2圖中對應於上述方法，本發明之氧化錫銦蝕刻廢液之回收再利用系統1〇0主要包含有一收集機構110、一陰離子交換機構120、一去陽離子交換機構13〇以及一濃度調配機才冓140。其中，氧化錫銦蝕刻廢液之回收路徑係以較粗線條標繪出。首先’進订「收集廢液」之步驟11。如第2圖所不，以該收集機構11〇收集已餘刻氧化錫銦之廢液，其中該廢液中係、包含有草酸根離子與金屬離子。在一具體實施例中廢液内金屬離子主要為：銦離子濃度在22〇〜5〇〇 Pfm，錫離子約4G〜12QPPm，録離子1〜2ppm，並包含非銦錫 S屬離子含夏為：鈉離子400〜2〇〇〇ppb，鋁離子〇 13〇〇PPb，鉀離子30〜260PPb，鐵離子約90ppb，鈣離子約33〇PPb、銷離子㈣4〇ppb，以及其它金屬離子，如鉻離子般金屬離子是以帶正電離子存在溶液中。但是在特薄古下會和其他分子結合以負離子存在，對於經濟效用奪面的鋼離子眚！^ 六姑不、上可以用正離子交換或負離子交換樹脂摩二：附。如表-所示，一個SKT2〇L的正離子交換樹脂^ 乂、吸附銦離子，銦離子的交換能力隨交換樹脂而不同 200815625 表一Consider step 14 and step H15 of "concentration blending". In the second figure, corresponding to the above method, the recycling system for the indium tin oxide etching waste liquid of the present invention mainly comprises a collecting mechanism 110, an anion exchange mechanism 120, a decation exchange mechanism 13 and a concentration. The blending machine is only 140. Among them, the recycling path of the indium tin oxide etching waste liquid is marked by a thick line. First, go to step 11 of “Collecting Waste”. As shown in Fig. 2, the waste liquid of the indium tin oxide is collected by the collecting means 11 , wherein the waste liquid contains oxalate ions and metal ions. In one embodiment, the metal ions in the waste liquid are mainly: indium ion concentration is 22〇~5〇〇Pfm, tin ion is about 4G~12QPPm, recorded ions are 1~2ppm, and non-indium tin S is contained in the ion containing summer. : sodium ion 400~2〇〇〇ppb, aluminum ion 〇13〇〇PPb, potassium ion 30~260PPb, iron ion about 90ppb, calcium ion about 33〇PPb, pin ion (tetra) 4〇ppb, and other metal ions such as chrome Ionic metal ions are in the presence of positively charged ions. However, in the ultra-thin, it will combine with other molecules to exist as negative ions, and the steel ions that are economically effective! ^ 六姑 No, you can use positive ion exchange or negative ion exchange resin. As shown in Table--, a positive ion exchange resin of SKT2〇L, adsorbed indium ions, and the exchange capacity of indium ions varies with exchange resin. 200815625 Table 1

Resin: SKT2 0L; Feed: In = 209.1ppmResin: SKT2 0L; Feed: In = 209.1ppm

Volume(mL) B.V. In(ppm) 草酸（％) 30 0.4 0.33 0.00426 60 0.9 4.31 0.01935 90 1.3 17.55 3.49768 120 1.7 35.91 3.74463 150 2.1 56.08 3.78051 180 2.6 78.85 3.77337 210 3.0 106.46 3.75436 240 3.4 123.78 3.76754 270 3.9 137.03 3.76875 300 4.3 138.55 3.74800 330 4.7 10.96 0.00373 9 200815625 表二Volume(mL) BV In (ppm) Oxalic acid (%) 30 0.4 0.33 0.00426 60 0.9 4.31 0.01935 90 1.3 17.55 3.49768 120 1.7 35.91 3.74463 150 2.1 56.08 3.78051 180 2.6 78.85 3.77337 210 3.0 106.46 3.75436 240 3.4 123.78 3.76754 270 3.9 137.03 3.76875 300 4.3 138.55 3.74800 330 4.7 10.96 0.00373 9 200815625 Table 2

Canacitv of Resins for In in ITO Etching Waste Solution (在ITO蝕刻廢液中樹脂對銦吸收力）Canacitv of Resins for In ITO Etching Waste Solution (resin absorption of indium in ITO etching waste)

Resin (樹脂） Capacity(g/mL Resin) Cation exchange (陽離子交換） SKT20L 0.00061 IRC748 0.00445 SP112 0.00086Resin (resin) Capacity (g/mL Resin) Cation exchange (cation exchange) SKT20L 0.00061 IRC748 0.00445 SP112 0.00086

Anion exchange (陰離子交換） >0.01100 >0. 01588 >0.00510Anion exchange >0.01100 >0. 01588 >0.00510

WA30LL MP62 IRA9 6 從表二可以看出來，負離子交換樹脂的對銦離子吸附能力會南於正離子交換樹脂，所以在本專利的回收IT〇的廢液步驟在「第一次去離子」之步驟12中，其係利用陰離子交換方式，使已蝕刻廢液通過該陰離子交換機構12〇之陰離子樹脂床，内填有陰離子型交換樹脂，其官能基可為三級胺或同時混合三級胺與四級胺之陰離子型交換樹脂，例如 Bayer公司提供之mP62、MP64、Mitsubishi公司提供之 200815625 WA30C、WA30LL、或是 ROHMANDHAAS 公司提供之 IRA 96。先以陰離子型交換樹脂吸附已蝕刻廢液内含之部分覃酸根離子。由於草酸根離子具有螯合基的特性，其性質可以將特定銦錫離子先行接合形成陰電性離子團。故能以被固著之草酸根離子螯合銦錫離子，達到高選擇性回收銦锡之功效。其反應機構如下： R+-_OH +(〇XC- )4In3+ —R+ —(OXC-)4ln3++ 〇『 R+--OKT + (OXC—)5 Sn4+ — R+ —(oxer )5 Sn4+ + ΟΗΓ 其中，R+表陰離子型交換樹脂，〇XC-表草酸根離子， In3 +表銦離子，Sn4+表錫離子。在一具體實施例中，經試驗，已蝕刻廢液内之銦離子可由220ppm降至2.0ppb以下’錫離子可由120ppm降至2.0ppb 左右，移除效率良好。另，上述之反應機構可由第3圖在床體積初期（<2 bed volume)草酸被吸收得到佐證，在過程（bed volume 1〜7)中銦離子維持在接近〇〇〇轴向，證明在上述之反應機構中高選擇性螯合銦離子之功效。以下為在「第一次去離子」之步驟12中蝕刻廢液通過床體積（B.V.)的金屬離子濃度之試驗數值： 11 200815625WA30LL MP62 IRA9 6 As can be seen from Table 2, the adsorption capacity of the negative ion exchange resin for indium ions will be souther than that of the positive ion exchange resin, so the waste liquid step of recovering IT〇 in this patent is in the "first deionization" step. In 12, the anion exchange method is used to pass the etched waste liquid through the anion resin bed of the anion exchange mechanism 12, and is filled with an anion exchange resin, and the functional group may be a tertiary amine or a mixed tertiary amine and Anionic exchange resins of quaternary amines, such as mP62, MP64 supplied by Bayer, 200815625 WA30C, WA30LL by Mitsubishi, or IRA 96 supplied by ROHMANDHAAS. First, an anion exchange resin is used to adsorb a part of the ruthenate ions contained in the etched waste liquid. Since the oxalate ion has a chelating group property, its properties can be prioritized by bonding a specific indium tin ion to form an anion group. Therefore, the indium tin ion can be sequestered by the immobilized oxalate ion to achieve high selectivity for the recovery of indium tin. The reaction mechanism is as follows: R+-_OH +(〇XC- )4In3+ —R+ —(OXC-)4ln3++ 〇『 R+--OKT + (OXC—)5 Sn4+ — R+ —(oxer )5 Sn4+ + ΟΗΓ where R+ Anionic exchange resin, 〇XC-epilycate ion, In3 + indium ion, Sn4+ tin ion. In a specific embodiment, it has been experimentally tested that the indium ions in the etched waste liquid can be reduced from 220 ppm to less than 2.0 ppb. The tin ions can be reduced from 120 ppm to about 2.0 ppb, and the removal efficiency is good. In addition, the above reaction mechanism can be confirmed by the absorption of oxalic acid in the initial stage of the bed volume (<2 bed volume) in Fig. 3, in which the indium ion is maintained close to the x-axis in the process (bed volume 1 to 7), which proves that The above-mentioned reaction mechanism has the effect of highly selective chelation of indium ions. The following is the test value of the metal ion concentration of the etching waste liquid passing through the bed volume (B.V.) in the first deionization step 12: 11 200815625

Resin ： MP62 金屬單位：ppbResin : MP62 Metal Unit: ppb

55.8 B.V.： 59.6 B.V.^ *3.5 B.V. 56.9B.V. Li <2.00 <2.00 <2.00 <2.00 Na 16.50 20.20 16.62 15.75 Mg 8.15 8.43 8.92 7.03 A1 3.27 2.19 2.36 2.07 K 6.15 11.00 6.87 9.02 Ca 287.12 295.18 304.87 263.06 Cr <2.00 <2.00 <2.00 <2.00 Mn <2.00 <2.00 <2.00 <2.00 Fe 5.17 4.46 11.14 4.45 Co <2.00 <2.00 <2.00 <2.00 Ni <2.00 <2.00 <2.00 <2.00 Cu <2.00 <2.00 <2.00 <2.00 Zn <2.00 3.47 3.62 4.35 Ga <2.00 <2.00 <2.00 <2.00 Sr 42.54 43.75 42.93 38.00 Ag <2.00 <2.00 <2.00 <2.00 Cd <2.00 <2.00 <2.00 <2.00 12 20081562555.8 BV: 59.6 BV^ *3.5 BV 56.9BV Li <2.00 <2.00 <2.00 <2.00 Na 16.50 20.20 16.62 15.75 Mg 8.15 8.43 8.92 7.03 A1 3.27 2.19 2.36 2.07 K 6.15 11.00 6.87 9.02 Ca 287.12 295.18 304.87 263.06 Cr <2.00 < 2.00 < 2.00 < 2.00 Mn < 2.00 < 2.00 < 2.00 < 2.00 Fe 5.17 4.46 11.14 4.45 Co < 2.00 < 2.00 < 2.00 < 2.00 Ni < 2.00 < 2.00 <2.00 < 2.00 Cu < 2.00 < 2.00 < 2.00 < 2.00 Zn < 2.00 3.47 3.62 4.35 Ga < 2.00 < 2.00 < 2.00 < 2.00 Sr 42.54 43.75 42.93 38.00 Ag < 2.00 < 2.00 < 2.00 < 2.00 Cd < 2.00 < 2.00 < 2.00 < 2.00 12 200815625

Ba 10.40 10.98 10.67 9.95 TI <2.00 <2.00 <2.00 <2.〇〇 Pb <2.00 2.58 3.08 3.32 Bi <2.00 <2.00 <2.00 ~~-—--- <2.〇〇 Sn 14.67 23.26 23.64 <2.〇〇 In <2.00 <2.00 5.51 <2.〇〇然後利用陰離子樹脂床再生的過程，將含銦錫離子的草酸螯合物廢水另外搜集回收至—高溫灰化機構i5G，以供姻錫之回收處理。之後，「第二次去離子」之步驟13中，將餘刻廢液導入至該去陽離子交換機構13G’用以去除該廢液中非銦錫金屬離子，而成為一更新液。 1 ^ 兵甲衹紊除之非銦錫金屬離子係至少包含有無離& . 匕各頁鈣離子（Ca 1〇n)與鳃離子（Sr ion)。其去離子方式可> 丁乃式』為％離子父換、物理過濾或兩Ba 10.40 10.98 10.67 9.95 TI <2.00 <2.00 <2.00 <2.〇〇Pb <2.00 2.58 3.08 3.32 Bi <2.00 <2.00 <2.00 ~~----- <2.〇〇Sn 14.67 23.26 23.64 <2.〇〇In <2.00 <2.00 5.51 <2. 〇〇 Then using an anion resin bed regeneration process, the indium tin ion-containing oxalic acid chelate wastewater is additionally collected and recovered to - The high-temperature ashing mechanism i5G is used for the recycling of the wedding tin. Thereafter, in the step 13 of the "second deionization", the residual waste liquid is introduced into the decation exchange mechanism 13G' to remove the non-indium tin metal ions in the waste liquid to become a refreshing liquid. 1 ^ The non-indium tin metal ion system that is only annihilated by the armor contains at least the separation of calcium ions (Ca 1〇n) and strontium ions (Sr ion). Its deionization mode can be used for "% cation", physical filtration or two

者之組合，即，上述繁-I 一-人去離子ν驟1 3係包含陽離 R* -H + 子型交換樹脂之離子交換或是精密過濾 (miCr^ltration)。在本實施例中，步驟13係採用陽離子型父換樹脂之離子交換’該去陽離子交換機構130 係包含-陽離子樹脂床，其内填充有陽離子型交換樹脂，例如Mitsubishi公司提供之SKT2〇L、或麵Μ娜 HAAS公司提供之IRC748 e其反應機構如下： Μ' H + 13 200815625 其中，R—表陽離子型交換樹脂，M+表锶、鈣等非銦錫金屬離子。以下為在本實施例中，蝕刻廢液在「第二次去離子」之步驟1 3之後金屬離子濃度之試驗數值：表四The combination of the above-mentioned complex-I-human deionization ν1 1 series includes ion exchange or precision filtration (miCr^ltration) of the cationic R*-H + subtype exchange resin. In the present embodiment, step 13 is an ion exchange using a cationic parent exchange resin. The decation exchange mechanism 130 comprises a bed of a cationic resin filled with a cationic exchange resin, such as SKT2〇L supplied by Mitsubishi. Or the reaction mechanism of IRC748 e provided by HAAS is as follows: Μ' H + 13 200815625 Among them, R-table cationic exchange resin, M+, non-indium tin metal ions such as strontium and calcium. The following is the test value of the metal ion concentration after the step 13 of the "second deionization" of the etching waste liquid in this embodiment: Table 4

Resin (樹脂）：SKT20LResin (resin): SKT20L

Feed : After MP62 5 8.8B.V. unit : ppb 5.1 B.V.： 5.0 B.V.< 8.1 B.V! 9.4 B.V. 11.3 B.V· Feed San Fu Spec Li <2.00 <2.00 <2.00 <2.00 <2.00 <2.00 <10 Na 39.79 15.55 14.98 17.86 41.29 15.75 <100 Mg <2.00 <2.00 <2.00 <2.00 <2.00 7.03 <20 A1 6.41 5.19 4.91 4.56 4.46 2.07 <20 K 13.54 13.80 8.74 10.39 5.31 9.02 <20 Ca 2.02 2.52 3.34 2.95 5.18 263.06 <50 Cr <2.00 <2.00 <2.00 <2.00 <2.00 <2.00 <50 Mn <2.00 <2.00 <2,00 <2.00 <2.00 <2.00 <10 Fe 11.59 11.56 9.93 9.54 11.13 4.45 <100 Co <2.00 <2.00 <2.00 <2.00 <2.00 <2.00 <10 Ni <2.00 <2.00 <2,00 <2.00 <2.00 <2.00 <50 Cu <2.00 <2.00 <2.00 <2.00 <2.00 <2.00 <10 Zn <2.00 <2.00 <2.00 <2.00 <2.00 4.35 <10 14 200815625Feed : After MP62 5 8.8BV unit : ppb 5.1 BV: 5.0 BV< 8.1 BV! 9.4 BV 11.3 BV· Feed San Fu Spec Li <2.00 <2.00 <2.00 <2.00 <2.00 <2.00 < 10 Na 39.79 15.55 14.98 17.86 41.29 15.75 <100 Mg < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 7.03 < 20 A1 6.41 5.19 4.91 4.56 4.46 2.07 < 20 K 13.54 13.80 8.74 10.39 5.31 9.02 < 20 Ca 2.02 2.52 3.34 2.95 5.18 263.06 <50 Cr < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 < 2.50 < 50 Mn < 2.00 < 2.00 < 2, 00 < 2.00 < 2.00 <2.00 <10 Fe 11.59 11.56 9.93 9.54 11.13 4.45 <100 Co < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 < 10 Ni < 2.00 < 2.00 < 2, 00 < 2.00 < 2.00 < 2.00 < 50 Cu < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 < 2.0 Zn < 2.00 < 2.00 < 2.00 < 2.00 < 2.00 4.35 <10 14 200815625

較佳地，上述回收i u ^ a e .dT來叹再利用方法，另包含有一過瀘/Preferably, the above-mentioned recovery i u ^ a e .dT is sighed and reused, and the other includes a

驟14，其係將該更轿&：A 尺新/夜導入至一過濾機構〗6 〇之過/應器，該過濾器可以使用pALL公司生產的濾芯蜇號 φ AB1VO〇23EHl或ABlv〇〇13EH1，以過濾該更新液之懸浮物。最後，在「濃度調配」之步驟1 5中，將更新液導入至該濃度調配機構1 4 0，在一攪拌槽丨4 i内可定量補充純水或/與高濃度草酸溶液，以使該更新液之草酸之濃度調配在lwt%至2〇wt%之間。更具體而言，在上述濃度調配步驟1 5中，以加入純水或草酸液方式，以使該更新液之草酸之濃度調配在2.0wt%至6.8wt%之間，可以選擇性使用FIR(Far Infrared)在線上監控，以供液晶 15 200815625 面板製造之用途。因此’在上述之氧化錫銦#刻廢液之回收再利用方法中’蝕刻廢液將回收成可完全再使用之氧化錫銦蝕刻溶液，無廢液排放之污染問題，深具產業利用性。此外，能高選擇性回收銦錫，以提高經濟價值。較佳地，上述回收再利用方法，另包含有一高溫灰化步驟1 6。如第2圖所示，在一高溫灰化機構！ 5 〇中，燃燒由上述第一次去離子步驟1 2取得之草酸螯合物，其以約600°C之高溫進行灰化，灰分能以酸消化分析得銦錫金屬含量，所得到之灰分係具有高於 50 wt %的銦成分與高於30wt %的錫成分。故由第一次去離子步驟1 2導出之草酸螯合物廢水係被灰化或是經由電解提煉（electrowinning)，亦無廢水排放問題。較佳地，由於銦與錫還原電位之不同，可進行一電解提煉（electr〇winning) 的步驟，利用銦與錫兩者元素電位差異，選擇性還原出高純度之銦，達到高價值的銦回收。以上所述，僅疋本發明的較佳實施例而已，並非對本發明作任何形式上的限制，雖然本發明已以較佳實施例揭露如上，然而並非用以限定本發明，任何熟悉本項技術者，在不脫離本發明之技術範圍内，所作的任何簡單修改、等效性變化與修飾，均仍屬於本發明的技術範圍内。【圖式簡單說明】第1圖：依據本發明之一具體實施例，一種氧化錫銦 16 200815625 蝕刻廢液之回收再利用方法之流程圖。第2圖：依據本發明之一具體實施例，一種氣化錫銦蝕刻廢液之回收再利用系統之設備示意圖。第3圖：為蝕刻廢液在本發明之第一次去離子步驟中之草酸與銦離子對照圖表。【主要元件符號說明】 11收集廢液 12第一次去離子步驟，以螯合銦錫離子 1 3第二次去離子步驟，用以去除非銦錫金屬離子 1 4過濾步驟 1 5 濃度調配 1 6 高溫灰化 I 00氧化錫銦蝕刻廢液之回收再利用系統 II 0收集機構 120陰離子交換機構 130去陽離子交換機構 140濃度調配機構 141攪拌槽 150高溫灰化機構 160過濾機構 17In step 14, it is to introduce the new car &:A ruler new / night into a filter mechanism〗 6 〇 / / /, the filter can use the filter element φ AB1VO〇23EHl or ABlv〇 produced by pALL company 〇13EH1 to filter the suspension of the update solution. Finally, in the step 15 of the "concentration adjustment", the update liquid is introduced into the concentration preparation mechanism 140, and the pure water or/and the high concentration oxalic acid solution can be quantitatively replenished in a stirred tank 4i to make the The concentration of the oxalic acid of the refreshing liquid is adjusted between 1% by weight and 2% by weight. More specifically, in the concentration setting step 15 described above, the pH of the oxalic acid of the refreshing solution is adjusted to be between 2.0% by weight and 6.8% by weight by adding pure water or oxalic acid solution, and the FIR can be selectively used. Far Infrared) is monitored online for use in LCD panel 1515615625 panel manufacturing. Therefore, in the above-mentioned method for recycling and recycling of indium tin oxide ingot, the etching waste liquid is recovered into a completely reusable tin oxide indium etching solution, and there is no pollution problem of waste liquid discharge, and it is industrially usable. In addition, indium tin can be recycled with high selectivity to increase economic value. Preferably, the above recycling method further comprises a high temperature ashing step 16. As shown in Figure 2, in a high temperature ashing mechanism! 5 〇, burning the oxalic acid chelate obtained by the first deionization step 12, which is ashed at a high temperature of about 600 ° C, and the ash can be analyzed by acid digestion to obtain the indium tin metal content, and the obtained ash is obtained. It has an indium component of more than 50 wt% and a tin component of more than 30 wt%. Therefore, the oxalic acid chelate wastewater derived from the first deionization step 12 is ashed or electrowinned, and there is no problem of wastewater discharge. Preferably, due to the difference in reduction potential between indium and tin, an electrorefining step can be performed to selectively reduce high-purity indium by using a difference in potential between the indium and tin to achieve high-value indium. Recycling. The above description of the preferred embodiments of the present invention is not intended to limit the scope of the present invention, and the present invention has been disclosed in the preferred embodiments, but is not intended to limit the present invention. Any simple modifications, equivalent changes and modifications made without departing from the technical scope of the present invention are still within the technical scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a method for recycling and recycling an etching waste liquid according to an embodiment of the present invention. Fig. 2 is a schematic view showing the apparatus for recycling and recycling a vaporized indium tin etching waste liquid according to an embodiment of the present invention. Figure 3: A comparison chart of oxalic acid and indium ions for etching waste liquid in the first deionization step of the present invention. [Main component symbol description] 11 Collect waste liquid 12 for the first deionization step to chelate indium tin ions 1 3 second deionization step to remove non-indium tin metal ions 1 4 filtration step 1 5 concentration preparation 1 6 high-temperature ashing I 00 indium tin oxide etching waste recycling system II 0 collection mechanism 120 anion exchange mechanism 130 to cation exchange mechanism 140 concentration adjustment mechanism 141 agitation tank 150 high-temperature ashing mechanism 160 filter mechanism 17

Claims

200815625 十、申請專利範圍： 1、一種氧化錫銦蝕刻廢液之回收再利用方法，包含：收集已蝕刻氧化錫銦之廢液，其中該廢液中係包含有草酸根離子；進行第一次去離子步驟，其係利用離子交換方式，先以陰離子型交換樹脂吸附草酸根離子，再以草酸根離子螯合銦離子（In i〇n)與錫離子（Sll ion); ❿ 進行第二次去離子步驟，用以去除該廢液中非銦錫金屬離子’而成為一更新液；以及進行一濃度調配步驟，以使該更新液之草酸之濃度調配在Iwt%至2〇wt%之間。 2、如申請專利範圍第丨項所述之氧化錫銦蝕刻廢液之回收再利用方法，另包含有一高溫灰化步驟，其係燃燒由上述第一次去離子步驟取得之草酸螯合物，所得到之灰分 _ 係具有高於50wt%的銦和高於30wt%的錫成分。 3、如申請專利範圍第1項所述之氧化錫銦蝕刻廢液之回收再J用方法，另包含有一電解提煉（electro winning)之步驟’以回收銦。 4如申明專利範圍第〖項所述之氧化錫銦蝕刻廢液之回收再利用方法’其中在上述第二次去離子步驟中，被去除之非銦錫金屬離子係至少包含有鈣離子（Ca i〇n)與錕離子（Sr ion) 〇 5、如申請專利範園第丨項所述之氧化錫銦蝕刻廢液之回收再利用方法，其中上述第二次去離子步驟係包含陽離子 200815625 型父換樹脂之離子交換。、如申請專利範圍第1或5 回收再利用方法，其中上密過濾（microfiitrati()r^。項所述之氧化錫銦蝕刻廢液之述第二次去離子步驟係包含精如申明專利範圍第〗項所述之氧化錫銦㈣廢液之回收再利用方法，其中在濃度調配步驟中，以加人純水或草200815625 X. Patent application scope: 1. A method for recycling and recycling tin oxide indium etching waste liquid, comprising: collecting waste liquid of etched tin indium oxide, wherein the waste liquid contains oxalate ions; The deionization step utilizes an ion exchange method to first adsorb an oxalate ion with an anion exchange resin, and then chelate the indium ion (In i〇n) with a tin ion (Sll ion) with an oxalate ion; a deionization step for removing non-indium tin metal ions in the waste liquid to become a refreshing liquid; and performing a concentration blending step to adjust the concentration of the oxalic acid of the refreshing liquid between 1 wt% and 2 wt% . 2. The method for recycling and recycling an indium tin oxide etching waste liquid according to the scope of the patent application, further comprising a high temperature ashing step of burning the oxalic acid chelate obtained by the first deionization step, The resulting ash _ has more than 50% by weight of indium and more than 30% by weight of tin. 3. Recycling of the indium tin oxide etching waste liquid as described in claim 1 of the patent application method, further comprising an electro winning step to recover indium. (4) A method for recycling and recycling tin oxide indium etching waste liquid according to the scope of the patent application, wherein in the second deionization step, the non-indium tin metal ion removed contains at least calcium ions (Ca I〇n) and 锟 ion (Sr ion) 〇5, as described in the patent application, the method for recycling and recycling the tin oxide indium etching waste liquid, wherein the second deionization step comprises a cation 200815625 type The father exchanged the ion exchange of the resin. For example, the patent application scope 1 or 5 recycling and recycling method, wherein the second deionization step of the indium sulphide etching waste liquid described in the microfiitrati () r ^ item includes the fine patent scope The method for recycling and recycling the indium tin oxide (IV) waste liquid according to item 7-14, wherein in the concentration preparation step, adding pure water or grass

酸液方式’以使該更新液之草酸之濃度調配在2 〇wt❶/〇至 6.8wt%之間。 8如申明專利範圍第i項所述之氧化錫銦蝕刻廢液之回收再利用方法，另包含有一過濾步驟，其係過濾該更新液之懸浮物。一種氧化錫銦蝕刻廢液之回收再利用系統，包含·· 一收集機構，用以收集已蝕刻氧化錫銦之廢液，其中該廢液中係包含有草酸根離子；一使用陰離子型交換樹脂之陰離子交換機構，以該陰離子型交換樹脂吸附草酸根離子，再以草酸根離子螯合銦離子（In ion)與錫離子（Sn ion); 一去陽離子交換機構，用以去除該廢液中非銦錫金屬離子，而成為一更新液；一過濾機構，用以去除該更新溶液之懸浮固體；以及一濃度調配機構，以使該更新液之草酸之濃度調配在 lwt% 至 20wt%之間。 1 〇、如申請專利範圍第9項所述之氧化錫銦蝕刻廢液之回收再利用系統，另包含有一高溫灰化機構，用以燃燒由 19 200815625 • 該離子交換機構取得之草酸螯合物。 ★ 11如申請專利範圍第9項所述之氧化錫銦蝕刻廢液之回收再利用系統，其中該去陽離子交換機構係使用陽離子型交換樹脂。 12、如申請專利範圍第8或10項所述之氧化錫銦蝕刻廢液之回收再利用系統，其中該去陽離子交換機構係具有精密過濾濾芯。 ® 13、如申請專利範圍第8項所述之氧化錫銦蝕刻廢液之回收再利用系統，另包含有一過濾機構具有過濾濾芯，用以過濾該更新液之懸浮物。 20The acid mode is such that the concentration of the oxalic acid of the refreshing liquid is adjusted between 2 〇wt❶/〇 and 6.8 wt%. 8 A method for recycling and recycling an indium tin oxide etching waste liquid as described in claim i, further comprising a filtering step of filtering the suspension of the refreshing liquid. A recycling system for indium tin oxide etching waste liquid, comprising: a collecting mechanism for collecting waste liquid of etched indium tin oxide, wherein the waste liquid contains oxalate ions; and an anion exchange resin is used An anion exchange mechanism for adsorbing oxalate ions by the anion exchange resin, and sequestering indium ions and tin ions with oxalate ions; a decation exchange mechanism for removing the waste liquid a non-indium tin metal ion to become a refreshing liquid; a filtering mechanism for removing suspended solids of the refreshing solution; and a concentration adjusting mechanism to adjust the concentration of the oxalic acid of the refreshing liquid between 1% by weight and 20% by weight . 1 〇, the recycling system of the indium tin oxide etching waste liquid described in claim 9 of the patent application, further comprising a high-temperature ashing mechanism for burning the oxalic acid chelate obtained by the ion exchange mechanism of 19 200815625 . The recycling and recycling system of the indium tin oxide etching waste liquid as described in claim 9 of the patent application, wherein the decation exchange mechanism uses a cationic exchange resin. 12. A recycling system for indium tin oxide etching waste as described in claim 8 or 10, wherein the decation exchange mechanism has a fine filter element. ® 13. The recycling system of the indium tin oxide etching waste liquid according to claim 8 of the patent application, further comprising a filtering mechanism having a filtering filter element for filtering the suspension of the updating liquid. 20