201219312 六、發明說明： 【發明所屬之技術領域】 、本發明是有關於-種高含料鐵之粗氧化辞處理 方法，特別是指一種粗氧化辞精煉處理方法。 【先前技術】 查’氧化鋅（ZnO)為一用途相當廣泛的金屬氧化 物，可應用於塑膠玉業、電子零件、塗料、藥品、及化 妝时等不同產業上，如在橡膠卫業上為重要的補強劑， 活性劑及硫化劑，也是白色膠料的著色劑與填充劑，因 它有提升橡膠耐磨性、耐撕裂性與彈性等優點；在印染 工業則作為印花防染劑，也可用於油漆、油墨、漆布的 著色上，如將氧化鋅添加於油漆中，對油漆的混合有很 大的幫助，且可以藉此控制稠度（c〇nsistency)、滲入度 (Penetration)和封閉性（seal ing)，進而改善油漆所形 成之薄膜的乾燥性與白堊性、減低其褪色及變黃程度， 以及增強其抗紫外線和防霉的特性。 再者，如結晶型態呈棒狀之氧化鋅，即一般所知的 一維氧化鋅，具有更高的經濟價值，結晶氧化辞被視為 種新型的半導體材料，其具有優異的光學與電學特 隹，目則已有务、外線探測器、發光二極體和半導體雷射 器等的氧化鋅半導體光電器件，此等器件可廣泛用於光 通信網路、光電顯示、光電儲存、光電轉化和光電探測 等領域，如此可知，氧化鋅已成為現在各產業中不可或 缺的原料之一。 201219312 然而，具高經濟價值的一維氧化鋅多半是由成本很 高的原生辞資源直接製得的，但近年來，環保意識提 昇，重視廢料再利用，而煉鋼廠所產生的集塵灰（electric arc furnace dust )廢料就因含有大量的鐵及辞之化合 物，已成為人們精煉鐵與鋅的重要來源之一；典型的集 塵灰包含氧化鐵、氧化鋅、氧化船、氧化鎂、氧化銅、 氧化納、氧化卸等數十種化合物，其中，該集塵灰含量 中的鋅與鐵約各佔20%wt左右；故為尋求成本較低之獲 得辞的方法，以及為使煉鋼廠廢料能有更好的再利用 性，人們試著利用各種方式從集塵灰中回收辞。 目前，在國外一般從集塵灰中回收鋅的方法均以火 法冶金方式進行，集塵灰經過高溫碳熱還原後，高揮發 性之辞與鉛可揮發而濃集於飛灰中，稱為粗氧化辞，其 辞含量可達到50%以上，所採用的技術與設備包含轉窯 爐法（Waelz process)、旋轉盤爐法（RHF)與多層爐法 (MHF);在台灣，煉鋼廠亦均以火法技術處理集塵灰， 使該集塵灰變成鋅含量較高的粗氧化鋅（Crude ZnO) 後，再以低價之次級原料轉售給煉鋅業與鋅化學製品 業，進行後續之精煉處理。 一般粗氧化鋅精煉之技術略可分為濕法與火法冶 金兩大類；例如於火法冶金中，雖有ISP豎井爐、電弧 爐、直立甑與水平甑等不同流程，但在粗氧化鋅精煉應 用上以ISP豎井爐為主流，主要以碳熱還原為基礎之火 法技術，其具有高回收率以及對原料雜質容忍度高等特 5 201219312 由於所需投資設備成本較大，且高溫耗損能源多 因素，需要處理非常大量之粗氧化鋅方可符合成本。 氣仆咎择在°又備及成本考量上’一般常以濕法進行該粗 =辞精練處理方法，参閱圖，，其包含有一備料步驟 一单階段浸潰步驟12、淨化㈣13及—結晶步驟 /其中’該備料步驟11係具備有-火法處理後所得之 粗乳化鋅’該單階段浸潰步驟12則利用—強酸液（如 硫酸)，以利用該強酸液與粗氧化鋅混合，產生含有硫 酸辞、硫酸鐵以及其他雜質之浸潰液及㈣，於該淨化 驟3中再利用雙氧水除鐵成分後，以辞粉去除銅編， 再以高猛酸鉀氧化劑去除鍾，並後續在該結晶步驟Μ 中將該混合液進行結晶處理，使該氧化辞從該混合液 中分離出，即完成該粗氧化鋅之精煉。 然，前述該粗氧化辞精煉處理方法丨具有下列缺失 產生： .由於該粗氧化鋅成分中鐵（〇 5~1〇%)、鉛（5~13%)及氣 (2.5 12%)等雜質含量相當高，且加上於該浸潰步驟前 並未先將該鐵與氯加以分離、去除，使得該浸潰步驟 所產出之殘渣内混有有害物質，導致該殘渣難以進行 再回收使用’甚至造成環境污染。 2.查，平均處理每一公噸之粗氧化鋅相對會產生一公頓 之殘渣，故該殘渣係屬有害事業廢棄物，雖含有大量 之鐵與錯成为’但因含紹之濕殘渣回收不易’故將該 殘渣當廢棄物丟棄時’另需額外進行固化處理，除造 201219312 成費用成本1¾、環境負荷大外，更是鐵、鉛等資源的 浪費。 3.再者，由於該粗氧化辞中鐵成分中含有難溶性之辞鐵 尖晶石（ZnFe204)，其必須用大量之強酸液，方能破 壞部分較難溶之辞鐵尖晶石，故若以單階段式浸潰進 行會造成酸用量大，不但會衍生出大量廢酸，導致處 理成本及環境負荷均提高，亦有待改進。 【發明内容】 因此，本發明之目的，是在提供一種粗氧化辞精煉 處理方法，其能有效降低精煉過程之處理成本外，同時 增加有價之金屬副產物產出，相對減少有害物質殘渣 里，以達到資源有效利用及環保等功效。 於是，本新型粗氧化辞精煉處理方法，其依序包含 有備料步驟、擦洗步驟、分級步驟、浸潰步驟及結晶锻 燒步驟；其中，該擦洗步驟中將粗氧化辞與水進行混 拌，使附著於該等粗氧化辞表面之含氯鹽類雜質因相互 碰撞溶解而去除，再將該等粗氧化辞依粒徑大小進行分 選（即分級步驟），以區分出含鐵成分多之重礦及含錯辞 成分多之輕礦，最後利用該浸潰步驟中之不同酸驗值的 硫酸溶液進行浸潰，以分別處理前述分選以同含量之 粗氧化鋅’除可減少該浸潰步財硫酸之使用量外，以 達到成本之降低外’同時將可使毒性較高之錯濃集至硫 酸錯泥中，避免與鐵混合，以達到殘渣量減少外同^ 該殘渣内所含之鐵及錯成分，亦可於該浸潰步驟及後續201219312 VI. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for processing a crude oxidation of high-content iron, and more particularly to a method for refining crude oxidation. [Prior Art] Check that zinc oxide (ZnO) is a widely used metal oxide, which can be applied to various industries such as plastic jade, electronic parts, paints, pharmaceuticals, and make-up. An important reinforcing agent, active agent and vulcanizing agent, it is also a coloring agent and filler for white rubber, because it has the advantages of improving rubber wear resistance, tear resistance and elasticity; in the printing and dyeing industry, it is used as a printing anti-dyeing agent. It can also be used for the coloring of paints, inks and varnishes. For example, adding zinc oxide to the paint can greatly help the mixing of the paint, and can be used to control the consistency, the penetration and the closure. Sealing, which improves the dryness and chalkiness of the film formed by the paint, reduces its fading and yellowing, and enhances its resistance to UV and mildew. Furthermore, zinc oxide, which is a rod-like crystalline form, is generally known as one-dimensional zinc oxide, and has higher economic value. Crystalline oxidation is regarded as a novel semiconductor material with excellent optical and electrical properties. In particular, the company has existing zinc oxide semiconductor optoelectronic devices such as external detectors, light-emitting diodes and semiconductor lasers. These devices can be widely used in optical communication networks, photoelectric displays, photoelectric storage, and photoelectric conversion. In the fields of photoelectric detection and so on, it is known that zinc oxide has become one of the indispensable raw materials in various industries. 201219312 However, most of the high-value one-dimensional zinc oxide is directly produced by the costly original resources. However, in recent years, environmental awareness has increased, and waste recycling has been emphasized. The dust collected by steel mills has been collected. (electric arc furnace dust) has become one of the important sources of refined iron and zinc because of the large amount of iron and compound compounds. The typical dust collection ash contains iron oxide, zinc oxide, oxidation vessel, magnesium oxide, Dozens of compounds, such as copper oxide, sodium oxide, and oxidative unloading, wherein zinc and iron in the dust ash content each account for about 20% by weight; therefore, it is a method for seeking lower cost, and for refining Steel mill waste can be better reused, and people try to use various methods to recover words from dust collection ash. At present, the methods for recovering zinc from dust collection ash in foreign countries are all carried out by pyrometallurgical method. After the high-carbon carbothermic reduction of the dust-collecting ash, the high volatility and lead can be volatilized and concentrated in the fly ash. Known as crude oxidation, its content can reach more than 50%. The technology and equipment used include the Waelz process, the rotary disk furnace (RHF) and the multi-layer furnace (MHF); in Taiwan, the steel mill The dust ash is also treated by fire technology, and the dust ash is turned into crude zinc oxide (Crude ZnO) with high zinc content, and then resold to low-cost secondary raw materials to the zinc industry and zinc chemical industry. , for subsequent refining treatment. Generally, the technology of crude zinc oxide refining can be divided into two major categories: wet method and pyrometallurgy; for example, in pyrometallurgy, although there are different processes such as ISP shaft furnace, electric arc furnace, vertical crucible and horizontal crucible, but in the crude zinc oxide Refining applications are mainly based on ISP shaft furnaces, mainly based on carbothermal reduction, which have high recovery rate and high tolerance to raw material impurities. 201219312 Due to the high cost of investment equipment and high temperature depletion energy Multi-factor, need to deal with a very large amount of crude zinc oxide to meet the cost. The gas servant chooses the ° and the cost considerations. Generally, the coarse scouring process is usually carried out by the wet method. Referring to the figure, it includes a preparation step, a single-stage impregnation step 12, purification (four) 13 and crystallization. Step / wherein 'the preparation step 11 is provided with the crude emulsified zinc obtained after the fire treatment'. The single-stage impregnation step 12 utilizes a strong acid liquid (such as sulfuric acid) to mix with the crude zinc oxide using the strong acid solution. Producing an impregnation liquid containing sulfuric acid, iron sulfate and other impurities, and (4), after removing the iron component by using hydrogen peroxide in the purification step 3, removing the copper braid by using the powder, and removing the clock with the high acid potassium oxidant, and subsequently The mixed solution is subjected to crystallization treatment in the crystallization step, and the oxidation is separated from the mixed solution to complete the refining of the crude zinc oxide. However, the above crude oxidation process refining method has the following defects: . Due to impurities such as iron (〇5~1〇%), lead (5-13%) and gas (2.512%) in the crude zinc oxide component. The content is quite high, and the iron and chlorine are not separated and removed before the impregnation step, so that the residue produced in the impregnation step is mixed with harmful substances, which makes the residue difficult to recycle. 'Even even causing environmental pollution. 2. Check that the average treatment of each metric ton of crude zinc oxide will produce a residue of one ton, so the residue is a hazardous business waste, although it contains a large amount of iron and wrong become 'but it is difficult to recover from the wet residue containing 'When the residue is discarded as waste', additional curing treatment is required. In addition to the cost of manufacturing 201219312, the cost is 13⁄4, and the environmental load is large. It is also a waste of resources such as iron and lead. 3. Furthermore, since the iron component of the crude oxidation contains iron-soluble spinel (ZnFe204), it is necessary to use a large amount of strong acid solution to destroy some of the hard-to-dissolve iron spinel. If the single-stage impregnation is carried out, the amount of acid will be large, and not only a large amount of waste acid will be derived, but also the treatment cost and environmental load will be improved, and improvement is needed. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a crude oxidation refining treatment method which can effectively reduce the processing cost of a refining process, and at the same time increase the yield of valuable metal by-products and relatively reduce the residue of harmful substances. In order to achieve effective use of resources and environmental protection. Therefore, the novel crude oxidation refining treatment method comprises, in sequence, a preparation step, a scrubbing step, a classification step, an impregnation step and a crystallization calcination step; wherein, in the scrubbing step, the crude oxidation word is mixed with water, The chlorine-containing salt impurities attached to the surface of the rough oxidized particles are removed by colliding with each other, and the coarse oxidized particles are sorted according to the particle size (ie, the classification step) to distinguish the iron-containing components. Heavy mines and light mines with many erroneous components, and finally use the sulfuric acid solution of different acid values in the impregnation step for impregnation to separate the above-mentioned sorting with the same content of crude zinc oxide' to reduce the dip In addition to the use of sulphuric acid sulphuric acid, in order to achieve a reduction in cost, at the same time, the toxic high-error error can be concentrated into the sulphuric acid miscible mud, avoiding mixing with iron, so as to achieve a reduction in the amount of residue. Containing iron and wrong components, can also be used in the impregnation step and subsequent
S 7 201219312 處理中分離出’而形成有價之金屬回收物，進而達到資 源有效利用及環保之功效。 【實施方式】 有關本發明之前述及其他技術内容、特點與功效， 在以下配合參考圖式之較佳實施例的詳細說明中，將可 清楚的明白。 参閱圖2，本發明粗氧化鋅精練方法3依序包含有 備料步驟3卜擦洗步驟32、分級步驟33、浸潰步驟35、 淨化步驟36及結晶煅燒步驟37 ;其中，該備料步驟31 係備置附著有雜質之粗氧化辞，亦即本實施例該粗氧化 辞可為煉鋼過程所產生之集塵灰處理後所得之產品，例 如電弧爐集塵灰經碳熱還原法所得之產品，其内成分比 例依不同之廠商處理方式而有些許之差異，平均成分含 有鋅（40~·)、鐵（〇· 5 〜繼）、敍（5 〜13%)、氣（2 515%) 及其他雜質等。 仍續前述’該擦洗步驟32具備有一可提供強力攪 拌功能之-擦洗機（該擦洗機並非本發明之技術特徵， 故不詳述）’以將料粗氧化鋅與水以高㈣濃度方式 加以混合，且該固液比範圍為内，而混合後之 聚體以30(M_rpm間之轉速進行搜拌 '擦洗作業，以 使附著於料減化辞㈣之可雜雜質（如氣化納、 氣化鉀、氯化錯等）可經由授拌過程該等粗氧化辞相互 摩擦碰撞下而快速轉於水巾，藉此除去至少·以上 之氯；當,然’為使該擦洗步驟32中之雜質去除效果更 201219312 =’該等粗氧化鋅與水之混拌物中可適時添加有一助掉 為费：減鍅或乳化鋁磨球等)，而該助拌物之體積約 為漿體之〇, 5〜1· 5倍。S 7 201219312 Separated from the treatment to form a valuable metal recyclate, thereby achieving the effective use of resources and environmental protection. The above and other technical contents, features and advantages of the present invention will become apparent from the following detailed description of the preferred embodiments. Referring to FIG. 2, the crude zinc oxide scouring method 3 of the present invention sequentially includes a preparation step 3, a scrubbing step 32, a classification step 33, an impregnation step 35, a purification step 36, and a crystallization calcination step 37; wherein the preparation step 31 is The crude oxidation word with impurities attached thereto is prepared, that is, the crude oxidation word in the embodiment can be obtained by the dust collection ash process produced by the steelmaking process, for example, the product obtained by the carbothermal dust collection method by the carbothermal reduction method. The composition ratio of the ingredients varies slightly depending on the manufacturer's treatment. The average composition contains zinc (40~·), iron (〇·5~继), Syria (5~13%), gas (2 515%) and Other impurities, etc. Continuing with the foregoing, the scrubbing step 32 is provided with a scrubber capable of providing a strong stirring function (the scrubber is not a technical feature of the present invention, and therefore is not described in detail) to apply the crude zinc oxide and water in a high (four) concentration manner. Mixing, and the solid-liquid ratio range is within, and the mixed polymer is subjected to a scrubbing operation at a speed of 30 (M_rpm) so as to be attached to the material to reduce impurities (such as gasification, The vaporized potassium, chlorinated, etc. can be rapidly transferred to the water towel by the frictional collision of the coarse oxidation words through the mixing process, thereby removing at least the above chlorine; when, in order to make the scrubbing step 32 The impurity removal effect is more 201219312 = 'The coarse zinc oxide and water mixture can be added with a help at a timely time: reduced or emulsified aluminum grinding balls, etc.), and the volume of the auxiliary mixture is about slurry After that, 5~1·5 times.
、再者’該分級步驟33具備有一分級機，該分級機 可乂重力刀選技術之螺旋選礦或上流式流體分級，如利 用螺旋選礦機、流體分級機或是震波分級機等設備(圖 中未不出），以便針對前述該擦洗步驟32中所得之該等 粗氧化鋅録徑進行分級作#，㈣餘、細顆粒之該 等粗氧化鋅初步分離’以分選出含鐵量較高之重礦與含 鉛鋅量較高之輕礦等兩大類，當然為使該輕礦中含有鐵 成份之顆粒能夠更完全的分離，故針對分選後之該輕礦 得以再加設有一磁選步驟34，而該磁選步驟34具有一 可提供磁場強度為3000~2〇〇〇〇高斯之磁選機，以針對 該輕礦分選出高含鐵之著磁輕礦，以及高含鉛之非著磁 輕礦，而前述該著磁性輕礦可與該重礦混合，一併進入 該浸潰步驟35内進行處理。 仍續前述’該浸潰步驟35係分為一微酸浸潰351 及一強酸浸潰352 ;其中，該微酸浸潰351係利用一酸 驗值3.5至5.5之硫酸溶液進行處理該輕礦，因該輕礦 中並無含有鋅鐵尖晶石（ZnFe2〇4)，故僅需利用微酸浸 潰對該輕礦進行處理’就可將該輕礦處理成硫酸鋅 (ZnS〇4)溶液及硫酸鉛（PbS〇4)殘渣等；至於，該強酸浸 潰352係利用一酸驗值0至2之硫酸溶液，以針對含鐵 里尚之重礦與者磁輕礦進行浸潰處理，進而破壞該鐵成 201219312 分中之辞鐵尖晶石（ZnFe2〇4)，以便將該重礦純化成硫 酸辞（ZnS〇4)溶液及其他之殘渣等。 特別是，為使前述該硫酸鋅（ZnS〇4)溶液中之各項雜 質分離出來，故加設有一淨化步驟36,去除含於該硫酸 辞溶液中大部分之雜質，該淨化步驟36依序包括有曝 氣除鐵、鋅粉置換除銅鎘、氧化除錳等三大部分；其中， 該曝氣除鐵係指加入可使酸驗值升高之驗劑（如消石 灰、粗氧化辞或氧化鋅）並曝氣使鐵沉澱為氫氧化鐵及 赤鐵礦混合物；另，該鋅粉置換除銅鎘係指利用一鋅粉 加入該硫酸辞溶液中，使該硫酸鋅溶液中銅及鎘與該鋅 粉產生反應而沉澱；至於，該氧化除錳則前述等步驟處 理後之硫酸辞溶液加入一氧化劑（如高錳酸鉀），以控制 其氧化還原電位0RP在250~500mV範圍，使該硫酸辞溶 液中之錳成分與該氧化劑反應產生一沉澱物（二氧化錳 固體），藉此將大部分之猛成分予以去除。 最後，該結晶煅燒步驟37，係將前述步驟所得之硫 酸鋅（ZnS〇4)溶液進行結晶與煅燒相關之加工，以形成氧 化辞（ZnO)結晶，並提供作為各產業之鋅原料；至於， 該硫酸鉛（PbS〇4)殘渣，其可經由簡單之後續處理成一鉛 膏，以提供煉鉛或相關之產業進行運用，另，其餘含鐵 之殘渣，因該水洗、分級及磁選等步驟中已將大部分之 氯及鉛成份去除，該殘渣主要成分為鐵、矽、鋁及其他 雜質，因該殘渣中含鐵量至少有20%以上，故該等殘渣 可提供給煉鋼業者，進入煉鋼製程或鋼廠固雜料回收系 10 201219312 統中，進行鐵資源之回收β 以下為證實本發明粗氧化鋅處理方法確實可利用 二雜磁選步驟確實可以將含鐵、錯量高之粗氧化辞進 2，以及得到高純度之工業級氧化辞，故提出實驗 例加以證明 實驗例： 其採用之粗氧化鋅為電爐煉鋼集塵灰以火法流程Furthermore, the grading step 33 is provided with a classifier which can perform gravity beating or upflow fluid grading by gravity knife selection technology, such as using a spiral concentrator, a fluid classifier or a shock classifier (in the figure) No, in order to sort the coarse zinc oxide recordings obtained in the scrubbing step 32 as described above, (4) the preliminary separation of the coarse zinc oxides of the fine particles, to sort out the high iron content. There are two major categories of heavy ore and light ore with high lead and zinc content. Of course, in order to make the particles containing iron in the light mine more completely separated, a magnetic separation step can be added to the light ore after sorting. 34, and the magnetic separation step 34 has a magnetic separator capable of providing a magnetic field strength of 3000 to 2 angstroms to select a high-iron-containing magnetic light ore for the light ore, and a high-lead non-magnetic Light ore, and the aforementioned magnetic light ore can be mixed with the heavy ore and enter the impregnation step 35 for processing. Continuing the foregoing, the impregnation step 35 is divided into a micro acid impregnation 351 and a strong acid impregnation 352; wherein the micro acid impregnation 351 system is treated with a sulfuric acid solution having an acid value of 3.5 to 5.5 to treat the light ore. Since the light ore does not contain zinc iron spinel (ZnFe2〇4), it is only necessary to treat the light ore by micro-acid impregnation, and the light ore can be treated into zinc sulfate (ZnS〇4). Solution and lead sulfate (PbS〇4) residue, etc.; as for the strong acid impregnation 352 system using a sulfuric acid solution with a value of 0 to 2 for the impregnation treatment of the heavy ore and the magnetic light ore containing iron Further, the iron spinel (ZnFe2〇4) of the iron into 201219312 is destroyed to purify the heavy ore into a sulfuric acid (ZnS〇4) solution and other residues. In particular, in order to separate the impurities in the zinc sulphate (ZnS〇4) solution, a purification step 36 is added to remove most impurities contained in the sulfuric acid solution, and the purification step 36 is sequentially performed. Including aeration and iron removal, zinc powder replacement in addition to copper and cadmium, oxidation and manganese removal, etc., wherein the aeration and iron removal refers to the addition of an agent that can increase the acid value (such as slaked lime, crude oxidation or Zinc oxide) and aeration to precipitate iron into a mixture of iron hydroxide and hematite; in addition, the replacement of copper powder by copper and cadmium means adding a zinc powder to the sulfuric acid solution to make copper and cadmium in the zinc sulfate solution Precipitating with the zinc powder to form a precipitate; as for the oxidation and manganese removal, the sulfuric acid solution after the above-mentioned steps is added to an oxidizing agent (such as potassium permanganate) to control the oxidation-reduction potential of 0RP in the range of 250-500 mV. The manganese component of the sulfuric acid solution reacts with the oxidant to produce a precipitate (manganese dioxide solid) whereby most of the harsh components are removed. Finally, the crystallization calcination step 37 is a process of crystallization and calcination of the zinc sulfate (ZnS〇4) solution obtained in the foregoing step to form oxidized (ZnO) crystals, and provides zinc raw materials as various industries; The lead sulfate (PbS〇4) residue can be processed into a lead paste by simple subsequent treatment to provide lead smelting or related industries, and the remaining iron-containing residue, in the steps of washing, grading and magnetic separation Most of the chlorine and lead components have been removed. The main components of the residue are iron, antimony, aluminum and other impurities. Since the residue contains at least 20% iron, the residue can be supplied to the steel industry. Steelmaking process or steel mill solid waste recycling system 10 201219312 system, the recovery of iron resources β The following is to confirm that the crude zinc oxide treatment method of the present invention can indeed use the two-magnetic magnetic separation step can indeed be iron-containing, high-volume Oxidation exchanging 2, and obtaining high-purity industrial grade oxidation, so the experimental example is proposed to prove the experimental example: the crude zinc oxide used is the electric furnace steel dust collection ash to the fire process
處理後所得之產品’其成分重量百分比如下表所示 (註：一般粗氧化辞之辞含量均在50%以上，本發明特挑 選低时位之粗氧化鋅作為實施案例以彰顯本發明 長）。 'The product obtained after the treatment's component weight percentage is shown in the following table (Note: the general crude oxidation word content is above 50%, and the present invention selects the low-time crude zinc oxide as an implementation case to highlight the invention) . '
.擦洗步驟： 取上述粗氧化鋅與清水及助拌物（即氧化鍅磨球） 呈1.1.1加以混拌，最後再利用清水加以沖洗，所得 之該等粗氧化鋅的氯含量由7.5%降至1.1%，去除率 高達85%。 2.分級步驟： 則述擦洗後經清水稀釋後，即進入至一螺旋選礦 機中’經過分級後可得顏色較深之重礦與顏色較淺之 輕礦’而該重礦與輕礦之重量比約為1:2〇;經過採 樣分析’重礦中之鐵含量提升為25.8%，足見藉由濕Scrubbing step: taking the above crude zinc oxide and water and the auxiliary mixture (ie, cerium oxide ball) in a mixture of 1.1.1, and finally rinsing with water, the chlorine content of the crude zinc oxide obtained is 7.5%. It fell to 1.1% and the removal rate was as high as 85%. 2. Grading step: After the scrubbing, after dilution with water, it enters into a spiral concentrator. After grading, the heavy ore with lighter color and lighter color can be obtained. The heavy ore and light mine The weight ratio is about 1:2〇; after sampling analysis, the iron content in the heavy ore is increased to 25.8%, which is seen by the wet
S 11 201219312 式分級處理可將鐵成份集中之粗顆粒加 3.磁選步驟： w 1分級後所得之輕礦漿體㈣至—半連續式渴 2磁選設備中’而被磁場截留之物料為高含鐵磁 =，出流之礦漿料高含錯鋅之非著磁料，故著磁料 =非者磁料之重量比約為G 8:1;經過採樣分析鐵 、·^量中有76/β集中於著磁料’非著磁料中之鐵含量降 低至3%或更低’足見以濕式磁選方式㈣可將高含 鐵之鋅鐵尖晶石成分加以分離。 丨·浸潰步驟： (a)輕礦處理 將步驟3所得之非著磁輕鑛與稀硫酸液混合，授 拌均質化同時並調整邱至4〜4.5’待授拌至一定時 間後’令漿體以適當之濾紙過濾，得到殘渣與澄清液 兩部分；經過採樣分析’澄清液之含量分別為鋅 咖小鐵4_g/1，45mg/1、盆跑的、錯塒小 而殘渣XRD光譜分析則測得大部分為硫酸錯且硫酸 鉛含量為48%。 (b)重礦處理 將步驟2所得之重礦及步驟3所得之著磁輕礦與 硫酸液混合，授拌均質化同時並調整pH至〇. ， 待授掉至—㈣間後’令装體以適當之濾紙過遽，得 到殘造與澄清液兩部分；經過採樣分析，液體之含量 分別為鋅 80g/l、鐵 65〇〇n]g/1、銅 1〇〇mg/i、錳 12 201219312 167mg/l、紹4. 5mg/l，而殘渣XRD光譜分析則測得 少量矽、鋁、鐵等之氧化物，大部分為硫酸鉛，且硫 酸鉛含量為38%。 5. 淨化步驟： 將步驟4所得之澄清液混合進入淨化程序，程序 中包含： (a) 曝氣除鐵：藉由加入可使pH值升高之驗劑（如消石 灰、粗氧化鋅或氧化鋅），並曝氣使鐵沉澱為氫氧 化鐵及赤鐵礦混合物，經過濾後所得之沉澱物經分 析含鐵量為24 %。 (b) 辞粉置換除銅鎘：將鋅粉加入除鐵後之溶液中並同 時攪拌，待反應完全後且經過過濾即可得雜質沉澱 物，該沉澱物經過分析主要為銅與録之沉殿。 (c) 氧化除錳：於經過a與b處理之溶液加入如高錳酸鉀 之氧化劑，經反應完全後可得深色沉澱物，固液分 離後經過分析為二氧化錳固體。 如此經過a、b、c之淨化步驟，所得之純淨硫酸 鋅溶液成分辞濃度為95g/l，鐵、銅、鉛、鎘、錳等 雜質均低於5mg/l。 6. 結晶煅燒步驟： 於經過步驟5淨化後之溶液t加入碳酸鈉，且施 以慢速攪拌，以得到白色沉澱物為鹼式碳酸鋅，過濾S 11 201219312 The classification process can add coarse particles with concentrated iron components. 3. Magnetic separation step: The light mineral slurry obtained after the classification of w 1 (4) to the semi-continuous thirst 2 magnetic separation equipment is high in the material retained by the magnetic field. Ferromagnetic =, the outflow of the slurry is high with the wrong zinc, not the magnetic material, so the weight ratio of the magnetic material = non-magnetic material is about G 8:1; after sampling and analysis, the amount of iron, · ^ ^ 76 / β is concentrated in the magnetic material 'non-magnetic material, the iron content is reduced to 3% or lower'. It can be seen that the high iron-containing zinc iron spinel component can be separated by wet magnetic separation (4).丨·Immersion step: (a) Light ore treatment Mix the non-magnetic light ore produced in step 3 with dilute sulfuric acid solution, homogenize the mixture and adjust the Qiu to 4~4.5' to be mixed until after a certain period of time. The slurry is filtered with appropriate filter paper to obtain two parts of residue and clear liquid. After sampling and analysis, the content of the clear liquid is zinc coffee iron 4_g/1, 45mg/1, pot running, small error and XRD spectral analysis of the residue. Most of the measurements were determined to be sulfuric acid and the lead sulfate content was 48%. (b) heavy ore treatment, the heavy ore obtained in step 2 and the magnetic light ore obtained in step 3 are mixed with the sulfuric acid liquid, homogenized and simultaneously adjusted to pH ,., to be transferred to - (d) The body is passed through a suitable filter paper to obtain two parts of the residue and the clear liquid. After sampling and analysis, the liquid content is zinc 80g/l, iron 65〇〇n]g/1, copper 1〇〇mg/i, manganese. 12 201219312 167mg / l, 4. 5mg / l, and residue XRD spectral analysis measured a small amount of oxides of barium, aluminum, iron, etc., mostly lead sulfate, and lead sulfate content of 38%. 5. Purification step: Mix the clear liquid obtained in step 4 into the purification program. The procedure includes: (a) Aeration and iron removal: by adding an agent that can raise the pH (such as slaked lime, crude zinc oxide or oxidation) Zinc), and aerated to precipitate iron as a mixture of iron hydroxide and hematite, and the precipitate obtained after filtration was analyzed to have an iron content of 24%. (b) Desiccation replacement of copper and cadmium: Add zinc powder to the solution after de-ironing and stir at the same time. After the reaction is completed and filtered, the impurity precipitate can be obtained. The precipitate is mainly analyzed by copper and recorded. temple. (c) Oxygen removal by oxidation: an oxidizing agent such as potassium permanganate is added to the solution treated with a and b, and a dark precipitate is obtained after completion of the reaction, and the solid-liquid separation is analyzed to be a manganese dioxide solid. Thus, after the purification steps of a, b, and c, the obtained pure zinc sulfate solution has a concentration of 95 g/l, and impurities such as iron, copper, lead, cadmium, and manganese are all less than 5 mg/l. 6. Crystallization calcination step: adding sodium carbonate to the solution t purified after the step 5, and applying slow stirring to obtain a white precipitate as basic zinc carbonate, filtering
S 13 201219312 後將固體於高溫環境中進行煅燒，最後可得工業級氧 化鋅（.’二XRD刀析結果如圖3所示），故可證本發明確 實月b將粗氧化辞處理成高純度之氧化鋅結晶。 由上述之說明，本發明確實具有以下所列之優點與 功效： 1.本發明之粗氧化鋅先經由該擦洗步驟，將高固體濃度 之粗氧化辞漿體與助拌物，使得該等粗氧化辞之顆粒 因攪拌下而相互碰撞摩擦，藉以去除大部分附著於該 粗氧化鋅表面之可溶性雜質，可將70%以上之氯消 除，使後續上之處理上無氯鹽累積的現象外，同時採 用的高固體濃度漿體亦具有提高處理效率及縮短處 理時間的功效。 2·由於浸潰步驟前，先行利用分級、磁選步驟將具含鐵 虿咼及含鉛鋅量高之粗氧化辞分離，使該浸潰純化過 程中，只需針對該含鐵量高之粗氧化辞，進行強酸浸 潰作業，而高含鉛鋅之物料僅須進行微酸浸潰即可達 到溶出目標，除可提升反應效果外，更能減少該硫酸 之使用量及廢酸之排放量，致使處理成本降低外，同 時更能減低環境衝擊和能源耗用。 3.仍續前述，由於含鐵及含鉛成份之粗氧化辞，以於浸 潰步驟已先前經過分選，如此該浸潰步驟中將鉛濃集 至硫酸鉛泥中，避免與鐵及其他金屬混合，不但可以 達到有害污泥減溶減量外，同時也提供了將鉛污泥以 錯膏形式作為次級原料之功效產生。 14 201219312 4. 再者，經分級後之重礦與經過磁選的著磁輕礦，其内 部之錯辞含量已去除大部份，故當該重礦與著磁輕礦 再經該強酸浸潰後，所產生之浸潰液經過除鐵後產生 含鐵之殘渣’以使該殘渣可經由後續加工處理成氧化 鐵，或者進入煉鋼製程或鋼廠固雜料回收系統中，進 行鐵資源之回收。 5. 仍續前述，該微酸、強酸浸潰與純化後所產生之硫酸 鉛及含鐵殘渣皆可分別進行後續回收及利用，因此所 產生之有害殘渣量可大幅降低，除降低掩埋場負荷， 增加環境效益，更能節省殘渣處理成本，提升經濟效 益等功效產生。 歸納前述，本發明粗氧化鋅精煉處理方法，藉由先 將該粗氧化鋅進行擦洗與物理分選之模式，除可減少該 浸潰步驟中硫酸之使用量外，以達到成本之降低外，同 時將了使t性較尚之錯濃集至硫酸錯泥中，避免與鐵及 其他毒性較低金屬混合，以達到殘渣量減少外，同時該 殘渣内所含之鐵及鉛成分，亦可於該浸潰步驟分離出， 而形成有彳貝之金屬回收物，進而達到資源有效利用及環 保之功效’故的確能達到本發明之目的。 准以上所述者，僅為說明本發明之較佳實施例而 已，當不能以此限定本發明實施之範圍，即大凡依本發 明申請專利範圍及發明說明書内容所作之簡單等效變 /、乜飾，皆應仍屬本發明專利涵蓋之範圍内。 £ 15 201219312 【圖式簡單說明】 圖1是習知粗氧化鋅精煉處理方法之流程圖； 圖2是本發明一較佳實施之流程圖；及 圖3本發明所產製之氧化鋅產品XRD分析圖。 【主要元件符號說明】 3 粗氧化辞精煉處理方法 31 備料步驟 32 擦洗步驟 33 分級步驟 34 磁選步驟 35 浸潰步驟 36 淨化步驟 37 結晶煅燒步驟 351 微酸浸潰 352 強酸浸潰 16After S 13 201219312, the solid is calcined in a high temperature environment, and finally industrial grade zinc oxide can be obtained (the results of the 'X XRD knife analysis shown in Fig. 3), so that the invention can indeed treat the crude oxidation word into a high Pure zinc oxide crystals. From the above description, the present invention does have the advantages and effects listed below: 1. The crude zinc oxide of the present invention first passes the high solid concentration of the crude oxidized sulphur slurry and the co-mixture through the scrubbing step, so that the coarse The oxidized particles collide with each other by friction, thereby removing most of the soluble impurities attached to the surface of the crude zinc oxide, and more than 70% of the chlorine can be eliminated, so that the subsequent treatment does not accumulate chlorine salts. The high solids concentration slurry used at the same time also has the effect of improving processing efficiency and shortening processing time. 2. Before the impregnation step, the grading and magnetic separation steps are used to separate the crude oxidized iron containing iron strontium and lead and zinc, so that the impregnation and purification process only needs to be high for the iron content. Oxidation, for strong acid impregnation, and high lead and zinc materials only need to be slightly acid impregnated to achieve the dissolution target, in addition to improving the reaction effect, can reduce the use of sulfuric acid and waste acid emissions This will reduce the cost of treatment and at the same time reduce environmental impact and energy consumption. 3. Continuing the foregoing, due to the crude oxidation of iron and lead containing components, the impregnation step has been previously sorted so that lead is concentrated in the lead sulfate mud during the impregnation step, avoiding iron and other Metal mixing can not only achieve harmful sludge reduction and reduction, but also provide the effect of using lead sludge as a secondary raw material in the form of a wrong paste. 14 201219312 4. Furthermore, after the classification of the heavy ore and the magnetically-selected magnetic light mine, the internal error content has been removed, so when the heavy ore and the magnetic light mine are re-impacted by the strong acid Afterwards, the resulting impregnation liquid is subjected to iron removal to produce iron-containing residue 'so that the residue can be processed into iron oxide by subsequent processing, or enters a steelmaking process or a steel plant solid waste recovery system for iron resources. Recycling. 5. Continued as mentioned above, the lead acid and iron residue generated by the micro acid and strong acid impregnation and purification can be separately recovered and utilized separately, so that the amount of harmful residue generated can be greatly reduced, except for reducing the landfill load. Increase environmental benefits, save waste disposal costs, and improve economic efficiency. In summary, the crude zinc oxide refining treatment method of the present invention, by first scrubbing and physically sorting the crude zinc oxide, can reduce the amount of sulfuric acid used in the impregnation step to reduce the cost. At the same time, the t-sexual error is concentrated in the sulfuric acid miscible mud to avoid mixing with iron and other less toxic metals to reduce the amount of residue, and the iron and lead components contained in the residue can also be The impregnation step is separated, and the metal reclaimed material of mussels is formed, thereby achieving the effective use of resources and the effect of environmental protection, so that the object of the present invention can be achieved. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent of the scope of the invention and the contents of the description of the invention. Decorations are still within the scope of the invention patent. £15 201219312 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a conventional crude zinc oxide refining process; FIG. 2 is a flow chart of a preferred embodiment of the present invention; and FIG. 3 is a zinc oxide product XRD produced by the present invention. Analysis chart. [Main component symbol description] 3 Rough oxidation refining treatment method 31 Preparation step 32 Scrubbing step 33 Grading step 34 Magnetic separation step 35 Immersion step 36 Purification step 37 Crystallization calcination step 351 Micro acid impregnation 352 Strong acid impregnation 16