Ί295591 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】 國内斂鐵棚磁鐵製造商，由於鄰近中國大陸，原料取得較容易， 每年生產相當數量的敍鐵硼磁鐵，因此國内亦衍生為數眾多之廢鈥鐵 硼磁鐵，這些廢鈥鐵棚磁鐵含有價之歛金屬，具資源目收價值，然而 國内目前並無廢職獅鐵之處理設施與技術，另經查關有關敍鐵 侧磁鐵之專利，皆是針對鈥鐵硼磁鐵製造方法與技術，並未發現任何 與廢鈥鐵硼磁鐵資源回收相關之專利，如中華民國專利編號147344為 高耐蝕性Nd-Fe-B磁石之製造’中華民國專利編號122915〇為稀土元素 磁石之製法及鍍浴，另中華民國專利編號135152為稀土族合金之加工 方法及應用此方法之稀土族磁石之製造方法。故本發明可提供國内相 關業者回收處理廢鈥鐵硼磁鐵之依據。 【發明内容】 近年來磁學的發展相當迅速，磁性材料的應用也日漸增加，目前已 被廣泛用於各類電子儀器、科技產品以及其他相關產業上，因此磁性材 料的使用大大的提升了人類生活品質與科技進步。鈥鐵删磁鐵是目前各 種磁性材料中磁性能最高的一種，其各項磁性能皆相當優異，可進行各 種切削和鑽孔的加工，因此特別適合使用在需求高磁力而體積小的產品 7 1295591 與領域上，鈥綱磁鐵是由敍(Nd)、鐵(Fe)、_)和其它微量元素組成， 依現订的製造技術，錢鐵爛磁鐵中鈹金屬的重量比為大約佔％ %左 右，而鐵含量大約有60%，硼則大約佔1 %。 國内由於鄰近中國大陸，磁鐵製造商取得原料較為容易，每年製 造、生產、加工、裁切為數相當數量的鈥鐵删磁鐵，因此亦衍生為數眾 多的廢敍細顧，2004年國内廢敍鐵獅鐵估計廢棄量(含外國進口 ) 、”勺為75〇模/年左右’但隨著逐年鈦鐵爛磁鐵的應用日漸增多，產量以 每年20 %的趨勢增加，未來將會產生更多的廢鉉鐵爛磁鐵，這些廢棄 的鉉鐵硼廢料和磁鐵產品所含之鈥有價金屬，為雜產業或尖端產業不 可或缺的原料，如果這些钕有價金屬無法回收再利用，會造成整體資源 之浪費甚為可惜。 有鑑於此，本發明乃針對廢鈥鐵硼磁鐵中之歛有價金屬進行回收工 作，本發明内容主要是先將廢歛鐵硼磁鐵置於35〇它之加熱爐中Μ分 鐘，予以加熱脫磁，再將脫磁後之廢鈦鐵硼磁鐵研磨篩分至通過％ mesh (0.297mm)以下，再將此研磨篩分物以3N雜為浸潰液，固液 比為lg/50ml ’，文潰溫度為27°C，於超音波震盪器中浸潰溶姓15分鐘， 可獲得歛、鐵、调之最佳浸潰效果。再收集此最佳浸潰液以氫氧化納將 八pH值调整至〇.6，待沉澱完全後過濾，可得到高純度之氫氧化欽沉 殿物，以售予專業之鈥資源回收精煉廠。 另經過濾後含鐵、硼之濾液，再以氫氧化鈉將其？11值調整至u， 經沉澱過濾後，可獲得氳氧化鐵及硼之沉澱物，以售予專業之鐵、硼資 8 1295591 源回收精煉廠。廢鈥鐵硼磁鐵經本發明之資源再生方法處理後，可達成 鈥、鐵、硼資源回收再利用之目的。 【實施方式】 本發明之較佳方法示於第一圖，首先將收集之廢鈥鐵硼磁鐵丨（其 外觀如附件一所示），經脫磁2步驟以完全去除其磁力，亦即將其置於 350°C之高溫爐中15分鐘。再將去除磁力之磁鐵經研磨篩分3步驟至其 通過5〇 mesh (0.297mm)大小之篩網。再將此小於5〇 mesh之研磨篩分 物進行超音波浸潰溶姓4步驟，此超音波浸潰溶钱4步驟之操作條件 為：固液比=lg/50ml，浸潰溫度=2r>c，浸潰時間^5分鐘及浸潰溶姓 液=3N硫酸。經超音波浸潰溶餘4步驟後，可將固體中之鈥、鐵、硼浸 潰溶餘於溶液中，其鈥浸潰回收率為1〇〇%，鐵浸潰回收率為丨㈨％， 而删浸潰回收轉可高達99·47 %。再經過濾5步料以猶後，所收 制之浸潰液51中即含有鈹、鐵、補源物；而超音波浸潰溶钱錢 經過滤5所收集到之殘逢52，則可直接進行最終處置作或再利用^。 本發明將触集之浸潰液51進行調整ΡΗ值6步驟，調整ρΗ值6 步驟為使贱崎浸· 51之ρΗ侧整至α6，崎浸潰液51 中之鈥金屬形成沉澱物，而鐵及酬仍留存於溶液中，待經調整阳值 6後之pH調整浸潰液61反應完全後，將ρΗ調整浸潰液61進行過據7 步驟，經過濾7步雜，可得到含Nd(OH)3沉殿物72 (其外觀如附件二 所示），以售予專業之鉉資源回收精煉廠，其歛金屬之沉殿回收率可達 9 1295591 97 %’第二圖為浸潰液51在pH值〇〜1下，鈥、鐵、硼金屬之沉殺回 收率。 接著將經過濾7步驟後所收集之含鐵、硼濾液71進行調整pH值$ 步驟，調整pH值8步驟為將含鐵、硼濾液71以氳氧化鈉將其pH值調Ί295591 IX. Description of invention: [Technical field to which the invention belongs] This creation belongs to the field of environmental protection and waste resource recycling technology. [Prior Art] Domestic manufacturers of iron shed magnets, because of the proximity to mainland China, the raw materials are easier to obtain, and a considerable number of S-iron-boron magnets are produced every year. Therefore, many decomposed iron-boron magnets are also produced in China. The iron shed magnet contains the price of the metal, which has the value of the resources. However, there is no disposal facility and technology for the lion iron in the country, and the patents on the magnets of the iron side are also checked for the NdFeB magnet. Manufacturing methods and technologies, did not find any patent related to the recycling of waste NdFeB magnets, such as the Republic of China Patent No. 147344 for the manufacture of high corrosion resistant Nd-Fe-B magnets. 'Republic of China patent number 122915〇 is a rare earth element magnet. The preparation method and the plating bath, and the Republic of China Patent No. 135152 are a processing method of a rare earth alloy and a manufacturing method of the rare earth magnet using the same. Therefore, the present invention can provide a basis for the domestic related industry to recycle and treat the waste iron-iron-boron magnet. SUMMARY OF THE INVENTION In recent years, the development of magnetics has been quite rapid, and the application of magnetic materials has been increasing. Currently, it has been widely used in various electronic instruments, technology products, and other related industries, so the use of magnetic materials has greatly enhanced humanity. Quality of life and technological advancement. Neodymium-cut magnets are the most magnetic properties of various magnetic materials. They have excellent magnetic properties and can be processed for various cutting and drilling. Therefore, they are especially suitable for products with high magnetic force and small volume. 7 1295591 In the field, the scorpion magnet is composed of Syrian (Nd), iron (Fe), _) and other trace elements. According to the current manufacturing technology, the weight ratio of bismuth metal in the iron-iron magnet is about %%. Around, the iron content is about 60%, and boron is about 1%. Due to the proximity of mainland China, magnet manufacturers are relatively easy to obtain raw materials. They manufacture, produce, process and cut a large number of ferroniobium-deposited magnets every year. Therefore, they are also derived from numerous wastes. Tieshi iron estimates the amount of waste (including foreign imports), "spoon is 75 〇 / year or so" but with the increasing use of ferrotitanium magnets every year, the output increases by 20% per year, and will produce more in the future. The depleted iron rotten magnets, the valuable metals contained in these discarded NdFeB scraps and magnet products, are indispensable raw materials for the miscellaneous industry or cutting-edge industries. If these valuable metals cannot be recycled and reused, the overall resources will be created. In view of this, the present invention is directed to the recovery of the valuable metal in the waste NdFeB magnet, and the present invention mainly places the waste iron boron magnet in a heating furnace of 35 Μ. Minutes, demagnetize by heating, and then pulverize the demagnetized waste titanium-iron-boron magnet to the passage of % mesh (0.297mm), and then grind the sieve with 3N miscibility, solid-liquid The ratio is lg/50ml ', the temperature of the text is 27 ° C, and it is immersed in the ultrasonic oscillator for 15 minutes to obtain the best immersion effect of convergence, iron and adjustment. Then collect the best immersion liquid. The pH value of the eight is adjusted to 〇6 with sodium hydroxide, and after filtration, the high-purity hydrazine can be obtained for sale to a professional 鈥 resource recovery refinery. The filtrate of boron is adjusted to u with sodium hydroxide. After precipitation and filtration, a precipitate of cerium oxide and boron is obtained for sale to a professional iron and boron source 8 1295591 source recovery refinery. After the waste iron-boron magnet is treated by the resource regeneration method of the present invention, the purpose of recycling, recycling of iron, iron and boron resources can be achieved. [Embodiment] The preferred method of the present invention is shown in the first figure, and the collected waste is firstly collected. The iron-boron magnet 丨 (the appearance of which is shown in Annex 1) is demagnetized in 2 steps to completely remove the magnetic force, which is also placed in a high-temperature furnace at 350 ° C for 15 minutes. The magnetic removal magnet is then sieved by grinding. Step 3 to pass through a 5〇mesh (0.297mm) screen. The grinding sieve of less than 5 〇mesh is subjected to ultrasonic soaking and immersion 4 steps. The operating conditions of the ultrasonic wave impregnation and solvent-dissolving step 4 are: solid-liquid ratio = lg / 50 ml, impregnation temperature = 2r > c, dip The collapse time ^ 5 minutes and the impregnation solution = 3N sulfuric acid. After the ultrasonic wave is soaked in the 4 steps, the solid, the iron, the boron and the boron can be immersed in the solution, and the recovery rate of the ruthenium is immersed. For 1〇〇%, the recovery rate of iron immersion is 丨(9)%, and the recovery of immersion recovery can be as high as 99.47%. After filtering 5 steps, the immersion liquid 51 contained in the sample is contained.铍, 铁,补源物; and the ultrasonic wave soaked and dissolved money is filtered by the 5 collected residue 52, then the final disposal or reuse can be directly carried out. Adjust the ΡΗ value of 6 steps, adjust the ρ Η value of 6 steps to make the 贱 浸 · 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 51 After the pH adjustment of the immersion liquid 61 is completed, the reaction of the immersion liquid 61 is completed, and the ρΗ adjustment immersion liquid 61 is subjected to the 7 steps, and the Nd(OH)3 sedimentation substance 72 is obtained by filtering 7 steps. Its appearance is shown in Annex II), which is sold to the professional resource recovery refinery. The recovery rate of the sinking metal can reach 9 1295591 97 %. The second picture shows the dipping solution 51 at pH 〇~1. , sputum, iron, boron metal killing recovery rate. Then, the iron-containing and boron-containing filtrate 71 collected after the 7-step filtration step is adjusted to a pH value of 100 steps, and the pH value is adjusted to 8 steps to adjust the pH of the iron-containing and boron-containing filtrate 71 with sodium bismuth oxide.
整至11，以將含鐵、硼濾液71中之鐵、硼形成沉澱物，待經調整pH 值8後之pH調整浸潰液81反應完全後，再將其進行過濾9步驟，經 過濾9步驟後，可得到Fe (OH)3 + B沉澱物92 (其外觀如附件三所示）， 其鐵金屬之沉澱回收率可達99.89 %，硼金屬之沉澱回收率可達9947 ‘。第二圖為含鐵、棚渡液71在pH值1〜14下鐵、爛之沉殿回收率。 最後經過濾9後所留下之濾液91可直接進行最終處置1〇。 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·可回收廢歛鐵硼磁鐵中之有價鈥金屬。 2.達到廢钕鐵硼磁鐵資源再生利用與減量。 3·避免廢歛鐵硼磁鐵污染環境。 4.具安全性與進步性。 5·具工商界與產業界上利用價值。 &綜上所述，本發明誠已符合發明專利之申請要件，並依法提出申 請，析請鈞局審查委員麵，並賜予本發明專利權，實感德便。 【圖式簡單說明】 1295591 第一圖係本發明廢鈥鐵硼磁鐵之資源再生方法流程圖。 第二圖係浸潰液在pH值0〜1下鈥、鐵、硼之沉澱回收率。 第三圖係含鐵、硼濾液在pH值1〜14下鐵、硼之沉澱回收率。 附件一係本發明所使用之廢鈥鐵硼磁鐵外觀照片（未脫磁）。 附件二係本發明以調整pH法沉澱回收之含Nd(OH)3沉澱物外觀照片。 附件三係本發明以調整pH法沉澱回收之(Fe(OH)3+B)沉澱物外觀照片。 【主要元件符號說明】 無 11Up to 11, to form iron and boron in the iron and boron filtrate 71 to form a precipitate. After the pH adjustment of the pH value of 8 is adjusted, the leachate 81 is completely reacted, and then filtered for 9 steps, filtered 9 After the step, Fe (OH) 3 + B precipitate 92 (the appearance of which is shown in Annex III) can be obtained, and the precipitation recovery rate of the iron metal can reach 99.89%, and the precipitation recovery rate of the boron metal can reach 9947 '. The second figure shows the recovery rate of iron and rotten sinks in the iron and shed liquid 71 at pH 1~14. Finally, the filtrate 91 left after filtration 9 can be directly subjected to final disposal. In order to make the present invention more expressive and practical, the advantages of the present invention are as follows: 1. The valuable ruthenium metal in the waste iron-boron magnet can be recovered. 2. Recycle and reduce the amount of waste NdFeB magnet resources. 3. Avoid the waste of iron and boron magnets to pollute the environment. 4. Safe and progressive. 5. Use value in the business community and industry. In summary, the invention has met the application requirements of the invention patent, and submitted an application according to law, and asked the bureau to review the members and give the patent right of the invention. BRIEF DESCRIPTION OF THE DRAWINGS 1295591 The first figure is a flow chart of the resource regeneration method of the waste iron-iron-boron magnet of the present invention. The second graph shows the precipitation recovery of cerium, iron and boron at pH 0~1. The third figure shows the precipitation recovery of iron and boron at pH 1~14 with iron and boron filtrate. Attachment 1 is a photograph (not demagnetized) of the appearance of the waste NdFeB magnet used in the present invention. Annex II is a photograph showing the appearance of the precipitate containing Nd(OH)3 precipitated by the pH adjustment method of the present invention. Annex III is a photograph showing the appearance of a (Fe(OH)3+B) precipitate recovered by pH adjustment in the present invention. [Main component symbol description] None 11