200916552 九、發明說明： 【發明所屬之技術領域】 本創作屬於環魏觀廢棄物資源再生技術領域。 【先前技術】 螢光粉為映像管輯之主要元件、隨著映像管報廢數量之增 加，國内亦衍生為數眾多之廢映像管螢光粉，這些廢發光粉含有價 之銷、纪’鋅’轉金屬，具資源回收價值，然而目前國内所有經 我國環保署核准之合格廢映像管處理公司，主要是利用真空吸除之 方式將螢絲付_，再顧收集之錢紐送財害事業廢棄 物口化處理廠予以固化處理，並未進行廢勞光粉之資源 回收工作， 甚為可惜。 另經查並未魏_有與廢映像管螢光㈣源时相關之專 利，如中華民國公告編號㈣奶『螢光粉體及其製造方法』，其内 容主要係為-種螢光粉體製造之方法。另中華民國公告編號第 I26l〇65 W效率螢光粉及其製法』，其内容主要係為利用固態合成法 來製造營光粉體。另中華民國公告編號第12_6『脑石權石勞光 粕之製作方法』’其内谷主要係提供以滴加方式來混合陰離子溶液與 陽離子溶液’以製造勞光粉體。另中華民國公告編號第π伽4『一 種螢光粉之喷塗液及其喷塗方法』，其内容主要係為一種營光粉之喷 塗液，用於電子裝置之陽極構造。 —綜合上述結果得知，國内螢光粉體相關之專利，皆是針對映像 管勞光粉製造方法與技術，並未發現任何與廢映像管榮光粉資源回 200916552 收相關之方法或技術。 【發明内容】 王世界每年映像管顯示器產量大約為1.88億台，於2006年到 2010年前後，數位電視的開播及LCD(液晶顯示器)時代的來臨，將 使全球各地出現換機熱潮，意味著在未來1〇年内，全球擁有的十 幾億台映像管電視機及電腦都將不得不更換，因此將產生的龐大廢 棄映像管電腦螢幕與電視機，這些為數龐大之廢映像管經回收處理 後，亦將衍生大量之廢螢光粉，由於廢螢光粉含有價之銪、釔、鋅、 鋁等金屬，如無法回收再利用，將會造成整體資源之浪費，甚為可 惜’有鐘於此’本發明乃針對廢映像管螢光粉中之銪、釔、辞、紹有 價金屬進行資源回收工作。 本發明内容主要是先將所收集之廢映像管螢光粉以5〇 mesh (0.297mm)之篩網予以篩分，再將篩下物(_〇297mm)置於3N氫氧化 鈉浸潰液中，以固液比為7g/50ml，浸潰溫度為27°C，藉超音波震盪 浸潰溶蝕30分鐘，可獲得鋁完全浸潰溶出之效果，經過濾後此含 鋁之浸潰液經添加沉澱劑(36N硫酸），在沉澱劑(ml)/浸潰液(mi)為 2/1 ’可將浸漬液中之鋁沉澱成Al(OH)3予以完全沉澱回收。再收集 過濾後之含銪、釔、鋅濾渣，置於 12N硫酸浸潰液中，固液比為 lg/50m卜浸潰溫度為7〇U(：，以超音波震盪浸潰溶餘12〇分鐘，可 獲得銪、釔完全浸潰溶出及辞57%浸潰溶出之效果，然後收集含 销纪鋅’文潰液’將其添加硫乙醯胺沉澱劑，在沉澱劑(ml)/浸潰 200916552 液（）為1/1 ’以恆溫震盪水槽震篕7天，可將辞沉激成ZnS，予以 完全沉殿回收。H卜、ra、上 ^ 、、坐過濾後所得之含銪、紀浸潰液，再以氫氧化鈉 調正” PH值至4，經沉澱過濾後，可獲得含氫氧化銪及氫 之沉;殿物，以隹早奎餐 丁寻菜之銪、釔資源回收精煉廠。廢映像管螢光粉 、二本發明之資料生綠纽後可賴n 屬資源回收再利用之目的。 有^金 【實施方式】 本發明之較佳方法示於第一圖，首先將收集之廢映像管榮光粉1 '、^附錄所示）’以50mesh (0.297mm)大小之篩網經過篩2步 驟進行筛分。經過筛2步驟後所得之大於50 mesh之+ 50聰h筛上物 22可直接進行最終處置23。而經過篩2步驟後所得之小於50 mesh之 _5〇meSh師下物21則進行氫氧化納浸漬溶蚀3步驟，氫氧化鈉浸潰溶 餘3步驟之操作條件為：固液比=聊_、浸潰溫度々I '浸潰裝置= 超曰波震盈H、浸鱗間，分鐘及浸潰溶織=3N氫氧化鈉，經氣氧 化納浸潰溶们步戰，可朗射德獅驗潰祕於溶液中，再 經過據4步料以過额，可收制含喊液42。 為回收此3峨液42之!g金屬’ 75針對此含赠液a進行銘沉殿 5步驟’其操作條件為：沉殿劑㈣/浸潰液_ 、溫度=抓、沉 ;’以丨36N硫^及/議反應裝置唯溫振盪水槽，經如職$步驟後可 將含鋁_ 42巾.1()() %扣職回收，觸^ 6步料以過滤後， 200916552 所收集到之含航麟叫其外觀如附錄二所示），則可好專業之紹冶 煉廠62。峨顧6後所留下之驗a可直躺行最終處置&。 另虱氧化納浸潰溶餘3後再經過據4所收集到之含鶴'紀、辞遽渣 i則可進行硫酸浸潰缝7步驟，其操作條件為：固液比=ig/5〇mi、 ’溫度’t、浸餘置咳音波震盪器、_=i2Q分似浸潰溶姑 液’魏’經碰浸潰_ 7步驟後，可制财之銪、紀、辞浸 f 潰溶蝕於溶液中，其銪浸潰回收率為 100 %，釔浸潰回收率為100%， 而鋅浸潰回收率為57 %，再經萄8步驟予_顧，所收集到之含 過滤殘渣82，财直接進行最終處置83。 而經過遽8步撕收_之含銪、心鋅驗81巾含_、纪、 鋅等有價麵'，膽齡H舰液S1進行鋅纖9步驟，其操 作條件為：沉_㈣/浸潰液㈣=1/卜溫㈣。c、職勝怪溫振 盪^槽、續時間=7天及沉搬劑=飽和硫乙醯胺，經辞沉殿9步驟後可 V. 將3銪、紀、辞據液81中之辞1〇〇 %予以沉殿回收，經過減1〇步驟予 以顧後’所_狀讀職物H)⑽峨如晴三_)，則可售 予專業之鋅冶煉礙〗03。 經過據1〇所收集之含銪、紀滤液10卜則予以進行pH值調整 ,阳值調整11步驟為使用氫氧化鈉將含銪、紀遽液101之pH 值6周整至4 ’以將含销、域液101中之㈣有價資源形成Eu(0H)3 及卿)3予以沉殿回收，經過遽12步驟後，可得到含销、紀沉澱物121 (、觀如崎四所不），以售予專業之銪、記資源·處理廠丨3，經邱 12 200916552 值調整η步驟後’銪、釔金屬之沉澱回收率可達1〇〇 % ’最後經過濾 I2後所留下之濾液122可直接進行最終處置123。 為使本發明更加顯現出其進步性與實用性，兹將本發日月之優點列舉 如下： 1. 可回收廢映像管榮光粉中之有價銪、紀、辞、銘金屬。 2. 達到廢映像管螢输《再生_與減量之雙重目的。 3. 避免料細像管料赌練軌危t人體健康。 4·具安全性與進步性。 5.具工商界與產業界上利用價值。 练上所述’本發明誠已符合發明專利之申請要件，並依法提出申 請’祈請姆查委員，並辭本發_權，實感德便。 【圖式簡單說明】 第一圖係本發明「廢映像管螢麵資源再生」之實施流程圖。 【主要元件符號說明】 益 13200916552 IX. Description of the invention: [Technical field to which the invention belongs] This creation belongs to the field of waste material recycling technology of Weiweiguan. [Prior Art] Fluorescent powder is the main component of the image tube series. As the number of discarded tubes in the image tube increases, the domestic waste toner powder is also a large number of waste image tube powders. 'Transfer metal, with the value of recycling resources, but at present all the qualified waste image tube processing companies approved by China's Environmental Protection Agency, mainly use vacuum suction to pay the ash, and then collect the money to send wealth It is a pity that the business waste chemical treatment plant is curing and does not carry out the recycling of waste light powder. In addition, there is no patent related to the source of the waste image tube fluorescent (4), such as the Republic of China Announcement No. (4) milk "fluorescent powder and its manufacturing method", its content is mainly - a kind of fluorescent powder The method of manufacture. In addition, the Republic of China Announcement No. I26l〇65 W Efficiency Fluorescent Powder and Its Preparation Method, the main content of which is to use the solid state synthesis method to manufacture camping powder. In addition, the Republic of China Announcement No. 12_6 "How to make a brain stone weight stone 光 』" 'the inner valley mainly provides a mixture of an anion solution and a cation solution by a dropping method to manufacture a glaze powder. In addition, the Republic of China Announcement No. π gamma 4 "a kind of fluorescent powder spray liquid and its spraying method" is mainly used as a spray coating liquid for camping powder, and is used for the anode structure of an electronic device. - Based on the above results, it is known that the patents related to domestic fluorescent powders are directed to the method and technology for producing optical tube powder, and have not found any method or technology related to the waste image tube glory resources back to 200916552. [Inventive content] Wang World's annual production of image tube displays is about 188 million units. From 2006 to 2010, the advent of digital TVs and the advent of LCD (liquid crystal display) era will cause a global exchange boom, meaning In the next one year, more than one billion video TV sets and computers in the world will have to be replaced, so the huge waste image tube computer screens and TV sets will be produced. After these huge waste image tubes are recycled, A large amount of waste fluorescent powder will also be derived. Since the waste fluorescent powder contains metals such as antimony, antimony, zinc and aluminum, if it cannot be recycled and reused, it will cause waste of the whole resources. It is a pity that there is a The present invention is directed to resource recovery work for ruthenium, ruthenium, rhodium, and valence metals in the waste image tube phosphor powder. The content of the invention is mainly that the collected waste image tube phosphor powder is sieved by a sieve of 5 〇mesh (0.297 mm), and the undersize material (_〇297 mm) is placed in a 3N sodium hydroxide immersion liquid. In the middle, the solid-liquid ratio is 7g/50ml, the impregnation temperature is 27°C, and the aluminum is completely impregnated and dissolved by the ultrasonic shock immersion and erosion for 30 minutes. After filtering, the aluminum-containing impregnation solution is filtered. A precipitant (36N sulfuric acid) was added, and in the precipitant (ml) / impregnation solution (mi) was 2/1 ', the aluminum in the impregnation liquid was precipitated into Al(OH)3 to be completely precipitated and recovered. The filtered ruthenium, osmium and zinc slag were collected and placed in 12N sulfuric acid leaching solution. The solid-liquid ratio was lg/50m, and the immersion temperature was 7〇U (:, soaked in supersonic shock immersion 12〇 Minutes, the effect of leaching and dissolving of yttrium and yttrium and the dissolution of 57% of the leaching solution can be obtained, and then the zirconia precipitant is added to the sulphur-containing sulphate precipitation agent in the precipitating agent (ml)/dip. Crush 200916552 liquid () is 1 / 1 ' shocked by a constant temperature shock sink for 7 days, can be spurred into ZnS, and completely recovered from the temple. H Bu, ra, Shang ^,, and filtered, The immersion liquid is immersed in sodium hydroxide, and the pH value is adjusted to 4, and after sedimentation and filtration, the sink containing strontium hydroxide and hydrogen can be obtained; the temple material, the 隹 隹 奎 餐 寻 寻 寻 寻 寻 寻 寻 寻 铕 铕Recycling refinery. The waste image tube fluorescent powder and the second invention of the invention can be used for recycling and recycling of the resources. The method of the present invention is shown in the first figure. First, the collected waste image tube glory powder 1 ', ^ appendix) 'screened by 50 mesh (0.297 mm) screen through the sieve 2 step. After the sieving step 2, more than 50 mesh + 50 s h sieve can be directly subjected to the final treatment 23. After the sieving step 2, less than 50 mesh _5 〇 meSh under the 21 is oxidized. In the three steps of nano-impregnation and dissolution, the operating conditions of the three steps of sodium hydroxide impregnation are: solid-liquid ratio = chat_, impregnation temperature 々I 'impregnation device = super-chopper shock H, dip scale, minute and Immersion solubilization = 3N sodium hydroxide, after gas-gas immersion and immersion, we can strike the lion to test the secret in the solution, and then, according to the 4 steps, the excess amount can be collected. In order to recover this 3 sputum 42! g metal '75 for this containing gift liquid a to carry out the 5 steps of the Ming Shen Temple's operating conditions are: Shen Dian agent (four) / dipping solution _, temperature = grasp, sink;丨36N sulfur ^ and / / reaction device only temperature oscillating water tank, after the work of the step can be used to contain aluminum _ 42 towel.1 () () % deduction, touch ^ 6 steps to filter, 200916552 collected To include the appearance of the airliner as shown in Appendix II), it is good to smelt the refinery 62. After the inspection of the 6th, the test can be left straight and finally disposed of & Residue 3 After the collection of the cranes containing the cranes and the remnants of the slag, the 7 steps of sulfuric acid leaching can be carried out. The operating conditions are: solid-liquid ratio = ig/5〇mi, 'temperature' t, immersion Cough wave oscillator, _=i2Q is like impregnating sputum liquid 'Wei' through the impact of immersion _ 7 steps, can be used to make money, 纪, 辞 浸 f 溶 溶 溶 溶 溶 溶 溶 溶 溶 溶 溶 溶 溶 溶For 100%, the recovery rate of ruthenium immersion is 100%, and the recovery rate of zinc immersion is 57%. Then, the ash-containing residue is collected, and the final treatment is carried out 83.遽8 steps to remove _ 铕 铕, heart zinc test 81 towel contains _, Ji, zinc and other valuable surface ', biliary age H ship liquid S1 for zinc fiber 9 steps, the operating conditions are: Shen _ (four) / impregnation (4) = 1 / Bu Wen (four). c, occupation wins strange temperature oscillation ^ trough, continued time = 7 days and sinking agent = saturated thioacetamide, after the steps of the Shen Shen Hall 9 can be V. 3 words, Ji, lexical fluid 81 in the words 1 〇〇% will be collected in the Shen Dian, after a step of minus 1 to take care of the 'study of the job' H) (10) 峨如晴三_), then can be sold to the professional zinc smelting obstacles〗 03. After adjusting the pH of the lanthanum and kiln filtrate collected according to 1〇, the pH value is adjusted. The step of adjusting the positive value is to use sodium hydroxide to adjust the pH value of the lanthanum and sputum liquid 101 to 6' for 6 weeks. The (4) valuable resources in the pin and domain liquid 101 form Eu(0H)3 and Qing)3, which are collected by the Shen Dian. After 12 steps, the pin and the sediments 121 can be obtained (there are no observations). For sale to professional 铕, 记 resources·processing plant 丨 3, after the adjustment of η step by Qiu 12 200916552 value, the precipitation recovery rate of bismuth and bismuth metal can reach 1〇〇%, and finally left after filtering I2 The filtrate 122 can be directly subjected to final disposal 123. In order to make the present invention more progressive and practical, the advantages of the present day and month are listed as follows: 1. The valuable 铕, 纪, 辞, and Ming metals in the waste image tube glory powder can be recycled. 2. Achieve the dual purpose of the waste image tube "regeneration" and reduction. 3. Avoid the need to look at the tube and gamble the danger of human health. 4. Safety and progress. 5. Use value in the business community and industry. In the practice of the invention, the invention has met the application requirements of the invention patent, and submitted an application in accordance with the law, praying for the Mcha member, and resigning the _ right, the real sense of virtue. BRIEF DESCRIPTION OF THE DRAWINGS The first figure is a flowchart for implementing the "reproduction of the waste image tube facet resources" of the present invention. [Main component symbol description] Benefit 13