1245023 九、發明說明： 【發明所屬之技術領域】 本創作屬於環境保護及廢棄物資源再生技術領域。 【先前技術】 珅化鎵廢棄物主要是由半導體電子業所產生，屬於新興電子廢料， 目前國内尚未有任何專業廢社鎵處理公顿技術，林發明亦未發 現國外有成熟之處理技術’故本發明可提供_細業者處理解決坤 化鎵廢棄物之環境污染問題。 【發明内容】 近年來科技不斷的進步，許多以半導體作為基本元件之電子產品， 不斷地被研究開發出來，其中坤化鎵(GaAs)憑藉著高頻率、高電子遷 移率、低噪音等優越的特性，在料化合物半導财脫穎㈣。坤化 鎵化合物之應用細包含無線通訊系統、光纖、手機、衛星直播節目、 n*車防撞雷達纟鱗，未來麟朝向個人軌網路、·人通訊服務 的目標邁進，因此近年來_外有許多公司看料化鎵前景，積極投 入石申化鎵產業’以致魏鎵之相關產品陸續不斷的增加，隨著神化錄 產品陸續增加’其衍生之坤化鎵廢棄物亦會隨之增加，但_目前尚 無適當的貝源回收處理技術與機構，可以妥善處理回收這些含碎化錄 的廢棄物。 1245023 就崎價值方面，坤化鎵廢棄物巾之鎵金屬，其價袼約為⑼〜獅 美禮g ’、_收精煉的鎵金屬，可以出f進而獲取利潤；而就環境影 響方面’魏鎵廢棄物巾之坤屬毒性物質，其化合物具相當之毒害性， 必需進行更進-步安定化(無害化)的處理。有鑑於此，本發明乃是研發 •種方法可將石申化鎵廢棄物中的鎵金屬予以回收再利用，另將其所 含之有害坤(As)物質予以無害化處理。 本發明内容主要是簡式冶鍊法，在室溫下，將魏鎵廢棄物置 於氫氧化鈉(NaOH)與過氧化氫(邮2)之混和浸潰液中，予以浸潰工 小時’可達到魏鎵廢棄物㈣與鎵完全浸潰溶出之效果。再收集 坤、鎵完全浸潰溶出之浸潰液，以硫酸調整該浸潰液的pH值至18， D2EHPA (Di-2-ethylhexyl Phosphoric acid ^ C16H3502P)^^it^t /合媒萃取，溶媒萃取後之含鎵有機相以6N的硫酸(η^〇4)進行反萃 取，反萃取後的含鎵反萃取溶液，再利用結晶法，使其所含之鎵生 成iiiGaXSO4)5 · 12托0結晶，以售予專業之鎵金屬精煉廠，來獲取 利潤。另經溶媒萃取後的含砷水相溶液，則以氫氧化納^aOH)調整 pH值至11，再加入FeXSO4)3調整鐵坤比(Fe/As)至6，攪拌1小時後 過濾，可得安定的FeAs〇4⑻廢棄污泥，而經過濾後尚含砷的濾液， 再以Amberjet 4400 OH樹脂(Sigma Chemical co·)吸附去除殘留之 砷。砷化鎵廢棄物經本發明之資源再生方法處理後，可以避免坤污染 環境並達成鎵資源回收再利用之雙重目的。 【實施方式】 1245023 本發明之較佳方法示於第一圖，首先將收集之砷化鎵廢棄污泥j， 經烘乾、研磨、篩分2後，通過2〇mesh篩網後，置入氫氧化鈉+過氧 化氫浸潰3程序，浸潰程序中使用〇·5Ν之氫氧化鈉，並添加氧 化劑0.5 vol%過氧化氫(Η2。)做為浸潰劑，另砷化鎵廢棄物(固體)與浸 潰液(液體)之固液比為4g/l〇〇m卜浸潰攪拌轉速為2〇〇rpm，在室溫下 浸潰1小時，可將砷化鎵固體樣品中之砷與鎵1〇〇%浸潰出來成為液 相（請參閱如第二圖所示）。 完成浸潰程序且經過溏後，可以得到含鎵、珅離子的浸潰液％及 含鄰3 · Fe3Al2(Si〇4)3的殘;^查Μ二部分，浸潰後的殘㈣經收集後 可直接進行掩埋等最終處置32 ;而浸潰液33再經ρΗ值調整4，以硫 a_整浸親33之ΡΗ餘1_8後，會生成部分含鎵及奴峨41(請 參閱如第三圖所示），這些沉殿41可再經浸潰3程序進行回收其所含 之鎵及砷。 另調整pH值4後所獲得的溶液42 (pH值為i 8)經收集後，依體積 η 1的比綱萃取_油轉D2EHPA溶媒至5ν〇ι%)進行溶媒萃取 5 ’萃取時間為H、時，溶媒萃取5完成後，原水相溶液42中之錄金 屬會被萃取出，進人上層有_ 5丨，而原水相溶液42巾之魏不會被 萃取出，存留在下層水相52 (請參閱如第四圖所示）。將下層水相52 與上層有機相Μ分離後’其上層有機相51，再以6n的硫酸進行反萃 取6，反萃取6後可將原上層有機相51中之鎵反萃至水相犯，此時反 萃取6後麟之有_ Μ可再料輯萃取5之萃轉制，而反萃 1245023 取0後的水相62中之鎵含量佔原砷化鎵廢棄污泥i中鎵含量之80%。 接著再以結晶回收法7，以水浴隔水加熱，溫度控制為90°C，加-熱時間為3小時，以將水相62中之鎵離子形成固態鎵化合物，以利鎵 金屬之資源回收，反萃取後的水相62經結晶回收法7濃縮後會形成上 下兩層，其上層部分為濃縮液72,而下層部分為形成之固態鎵化合71， 上層濃縮液72主要為濃縮的硫酸，並且尚含少量的鎵，可經回流作為 反萃取6之反萃取劑使用，而下層為固態之含硫酸鎵的結晶化合物71， 其成分主要為H4Ga2(S〇4)5 · 12H20，經結晶回收法7回收後之含硫酸 _ 錄結晶71可售予鎵金屬精煉廠，以獲取利潤。整體而言砷化鎵廢棄物 污泥1，經浸潰3、溶媒萃取5、反萃取6及結晶回收法7後，其整體 錄回收率可達70%以上，而剩餘之鎵金屬如經多次溶媒萃取5、反萃取 6及結晶回收法7後，其鎵之整體回收率應可再提升。 - 另經溶媒萃取5後所得下層水相52中尚含有害砷物質，需進一步 處理’本發明將下層水相52予以進行珅無害化處理8，亦即以Μ· 凋整下層水相52之pH值至1卜再加入Fe2(s〇4)3調整鐵坤比(Fe/As) 至6，麟1小時後，可將珅予以沉澱，經過渡後可得安定之〇蝴 _ 沈版物81 ’而過遽後砂未完全沉殿之含珅溶液a，再以Amberjet44〇〇 OH樹脂(Sigma Chemical c〇 )進行離子交換9 ,經離子交換9後可謂 去除含呻溶液82巾之$，經無害化處理g及離子交換9後，坤的整體 去除率可達99·9"%。經離子交換9後所得離子交換溶液％之阳值 約為13.5，可將離子交換溶液％回流至石申無害化處理8程序中，做為 =整=值的調整，或亦可將其回流至氫氧仙+過氧化氫浸潰3程序， 田作/又/貝劑使用’如此含微量坤的離子交換溶液％可以循環再使用不 11 1245023 需排放。 而經離子交換9後產生之飽和樹脂92，可將此飽和樹脂92直接送 交專業之廢棄物處理公司予以最終處置。或者將飽和樹脂92進行反沖 洗，反沖洗後的樹脂仍可以再生使用，而反沖洗後產生之含坤的反沖 洗液的部分，則可進入砷無害化處理8程序再進行處理，最後含砷廢 液中的砷可100〇/〇以FeAs〇4W污泥型態產出，成為安定之廢棄污泥。第 五圖係本發明所使用之砷化鎵廢棄污泥外觀照片，第六圖係本發明以 結晶回收法回收之含硫酸鎵結晶照片，本發明之整體處理流程圖請查 閱第一圖所示。 為使本發明更加顯現出其進步性與實用性，茲將本發明之優點列 舉如下： 1·避免砷化鎵廢棄物污染環境。 2·達到廢棄物資源再生利用與減量。 3·具安全性與進步性。 4·具工商界與產業界上利用價值。 知上所述’本發明誠已符合發明專利之申請要件，並依法提出申 請’祈請鈞局審查委員明鑑，並賜予本發明專利權，實感德便。 【圖式簡單說明】 第一圖係本發明砷化鎵廢棄物資源再生方法方塊流程圖。 第二圖係本發明之坤、鎵溶解浸潰溶出率曲線圖。 第三圖係本發明以硫酸調整浸潰液pH值之砷、鎵沉澱率曲線圖。 第四圖係本發明溶媒萃取之砷、鎵萃取率曲線圖。 第五圖係本發明所使用之砷化鎵廢棄污泥外觀照片。 第六圖係本發明以結晶回收法回收之含硫酸鎵結晶照片。 121245023 IX. Description of the invention: [Technical field to which the invention belongs] This creation belongs to the technical field of environmental protection and waste resource regeneration. [Previous technology] Gallium tritide waste is mainly produced by the semiconductor electronics industry, which is a new type of electronic waste. At present, there is no professional waste treatment technology for gallium treatment in China, and Lin invention has not found mature treatment technology abroad. 'Therefore, the present invention can provide detailed solutions to the environmental pollution problems of Kunhua gallium waste. [Summary] In recent years, science and technology have continued to advance. Many electronic products that use semiconductors as basic components have been continuously developed. Among them, GaAs has high frequency, high electron mobility, and low noise. Characteristics, the compound of semi-finished material is outstanding. The application of Kunhua gallium compounds includes wireless communication systems, optical fibers, mobile phones, live satellite programs, n * car collision avoidance radar scales. In the future, Lin will move towards the goals of personal rail networks and human communication services. There are many companies looking at the prospect of gallium gallium and actively investing in the gallium industry of Shishenhua. As a result, the related products of gallium wei have continued to increase. With the continuous increase of divine products, the waste of gallium gallium derived from it will also increase, but _ At present, there is no proper shell source recovery and treatment technology and organization that can properly process and recycle these wastes containing crushed records. 1245023 In terms of saki value, the price of gallium metal from Kunhua's gallium waste towels is about ⑼ ~ Shimei Li g ', _ refining the refined gallium metal can generate f and then make a profit; and in terms of environmental impact' Wei The gallium waste towel is a toxic substance, and its compounds are quite toxic. It must be further stabilized (detoxified). In view of this, the present invention is to develop a method to recycle and reuse the gallium metal in Shishenhua gallium waste, and to detoxify the harmful substances contained in it. The content of the present invention is mainly a simple chain smelting method. At room temperature, weilium gallium waste is placed in a mixed dipping solution of sodium hydroxide (NaOH) and hydrogen peroxide (post 2) and immersed in working hours. To achieve the effect of Wei Ga gallium rubidium and gallium leaching and dissolution. Then collect the leaching solution completely dissolved by dissolving Kun and Gallium, and adjust the pH value of the leaching solution to 18 with sulfuric acid. D2EHPA (Di-2-ethylhexyl Phosphoric acid ^ C16H3502P) ^^ it ^ t / solvent extraction, solvent The extracted gallium-containing organic phase was back-extracted with 6N sulfuric acid (η ^ 〇4). The back-extracted gallium-containing back extraction solution was then crystallized to make the gallium contained in it into iiiGaXSO4) 5 · 12 Torr Crystallize to sell to a professional gallium metal refinery for profit. In addition, the arsenic-containing aqueous phase solution after solvent extraction is adjusted to pH 11 with sodium hydroxide ^ aOH), and then FeXSO4) 3 is added to adjust the iron-kun ratio (Fe / As) to 6. After stirring for 1 hour, it can be filtered. A stable FeAs04 waste sludge was obtained, and the filtrate that still contained arsenic after filtration was adsorbed to remove residual arsenic with Amberjet 4400 OH resin (Sigma Chemical co.). After the gallium arsenide waste is treated by the resource regeneration method of the present invention, it can avoid the pollution of the environment and achieve the dual purpose of recycling and reusing gallium resources. [Embodiment] 1245023 The preferred method of the present invention is shown in the first figure. First, the collected gallium arsenide waste sludge j is dried, ground, and sieved 2 and passed through a 20 mesh screen and placed in Sodium hydroxide + hydrogen peroxide impregnation procedure 3, sodium hydroxide of 0.5N is used in the impregnation procedure, and an oxidizing agent of 0.5 vol% hydrogen peroxide (Η2.) Is added as an impregnating agent, and gallium arsenide waste is added. The solid-liquid ratio of (solid) to the impregnating liquid (liquid) is 4 g / 100 m. The impregnating stirring speed is 2000 rpm, and the impregnating speed is 2000 rpm. 100% of arsenic and gallium leached out into a liquid phase (see Figure 2). After the impregnation procedure is completed and after thorium, we can obtain the gallium and thorium-containing impregnation solution% and the residue containing o-Fe3Al2 (Si〇4) 3; ^ Check M two parts, the residue after the impregnation is collected After that, it can be directly treated for final disposal such as burial 32; and the impregnating solution 33 is adjusted by ρΗ value 4 to sulphur a_ to immerse the proton 33 and the remaining 1_8, and some gallium-containing and slave 41 (see As shown in the three pictures), these sinking halls 41 can be recovered through the immersion 3 process to recover their gallium and arsenic. In addition, the solution 42 (pH value i 8) obtained after adjusting the pH value 4 was collected, and then subjected to solvent extraction according to the volume η 1 ratio extraction_oil to D2EHPA solvent to 5 v%), and the extraction time was H At this time, after the solvent extraction 5 is completed, the metal recorded in the original aqueous phase solution 42 will be extracted, and the upper layer will be _ 5 丨, and the Wei of the original aqueous phase solution 42 will not be extracted, and will remain in the lower aqueous phase 52 (See Figure 4). After separating the lower aqueous phase 52 from the upper organic phase M, the upper organic phase 51 thereof is subjected to back extraction 6 with 6n sulfuric acid. After the back extraction 6, the gallium in the original upper organic phase 51 may be back extracted to the aqueous phase. At this time, after the back-extraction of 6, the _M can be re-extracted to the extraction of 5 extraction, and the back-extraction of 1245023 is 0. The gallium content in the water phase 62 accounts for 80% of the gallium content in the original gallium arsenide waste sludge %. Then, the crystallization recovery method 7 is adopted, and the water bath is used to heat the water, the temperature is controlled to 90 ° C, and the heating-heating time is 3 hours, so as to form the gallium ion in the water phase 62 into a solid gallium compound for the recovery of the resources of gallium After the water phase 62 after the back extraction is concentrated by the crystallization recovery method 7, two upper and lower layers are formed. The upper part is the concentrated liquid 72, and the lower part is the formed solid gallium compound 71. The upper concentrated liquid 72 is mainly concentrated sulfuric acid. And it still contains a small amount of gallium, which can be used as the back-extractant of back-extraction 6 under reflux, and the lower layer is a solid gallium sulfate-containing crystalline compound 71, whose main component is H4Ga2 (S〇4) 5 · 12H20, which is recovered by crystallization. Sulfuric acid-containing crystal 71 recovered after method 7 can be sold to a gallium metal refinery for profit. On the whole, the gallium arsenide waste sludge 1 was subjected to leaching 3, solvent extraction 5, back extraction 6 and crystallization recovery method 7, and the overall recovery rate was over 70%. After secondary solvent extraction 5, back extraction 6 and crystallization recovery method 7, the overall recovery of gallium should be improved. -In addition, the lower aqueous phase 52 obtained after solvent extraction 5 still contains harmful arsenic substances, which needs to be further processed. 'The present invention performs the innocuous treatment 8 of the lower aqueous phase 52, that is, the lower aqueous phase 52 is withered. Add pH2 to Fe2 (s〇4) 3 and adjust iron-kun ratio (Fe / As) to 6. After 1 hour, plutonium can be precipitated. After the transition, it will be stable. 81 'And after the sand has not completely settled, the thorium-containing solution a, and then Amberjet 44OOOH resin (Sigma Chemical Co) for ion exchange 9, after the ion-exchange 9 can be said to remove the thorium-containing solution 82 dollars, After harmless treatment of g and ion exchange 9, the overall removal rate of Kun can reach 99.9%. The ion value of the ion exchange solution% obtained after ion exchange 9 is about 13.5, and the ion exchange solution% can be refluxed to the Shishen harmless treatment 8 program as an adjustment of the value of = integer =, or it can be refluxed to Oxygen + hydrogen peroxide impregnation 3 procedures, Tiansaku / you / shellfish use 'so that the ion exchange solution containing a small amount of Kun can be recycled and reused without 11 1245023 need to be discharged. The saturated resin 92 produced after ion exchange 9 can be directly sent to a professional waste disposal company for final disposal. Or the saturated resin 92 is backwashed. The resin after backwashing can still be reused, and the part of the backwashing liquid containing Kun after the backwashing can be processed into the arsenic detoxification process 8 and then processed, and finally contains arsenic The arsenic in the waste liquid can be produced at 100/0 in the form of FeAs〇4W sludge, and becomes a stable waste sludge. The fifth picture is an appearance photo of the gallium arsenide waste sludge used in the present invention, and the sixth picture is a photo of the gallium sulfate-containing crystal recovered by the crystallization recovery method of the present invention. Please refer to the first picture for the overall processing flow chart of the present invention. . In order to make the present invention more show its progress and practicability, the advantages of the present invention are listed as follows: 1. Avoid gallium arsenide waste from polluting the environment. 2. Achieve recycling and reduction of waste resources. 3. With safety and progress. 4. Utilization value in business and industry. Knowing the above ‘this invention has already met the application requirements for invention patents, and filed an application in accordance with the law’, I ask the jury ’s reviewing committee to make a clear reference and grant the invention patent right. [Brief description of the drawings] The first diagram is a block flow chart of the method for regenerating gallium arsenide waste resources according to the present invention. The second figure is a graph of the dissolution rate of dissolution and leaching of kun and gallium in the present invention. The third figure is a graph of the arsenic and gallium precipitation rates of the present invention for adjusting the pH value of the infusion solution with sulfuric acid. The fourth graph is a graph of arsenic and gallium extraction rate extraction by the solvent extraction of the present invention. The fifth figure is an appearance photo of the gallium arsenide waste sludge used in the present invention. The sixth figure is a photograph of gallium sulfate-containing crystals recovered by the crystal recovery method of the present invention. 12