1377178 六、發明說明： 【發明所屬之技街領域】 本發明是㈣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】 °1377178 VI. Description of the invention: [Technical street field to which the invention belongs] The present invention is a method for processing a crude oxidation of iron in a high-content iron, in particular, a method for refining crude oxidation. [Prior Art] °
查，氧化鋅（Zn〇)為一用途相當廣泛的金屬氧化 物，可應用於塑膠工業、電子零件、塗料、藥品、及化 妝品等不同產業上’·如在橡膠工業上為重要的補強劑， 活性劑及魏’也是自色膠料的著色㈣填充劑因 它有提升橡料純、耐撕肢_性等優點；在印染 =業則作為印花防染劑，也可用於油漆、油墨、漆布的 者色上；如將氧化辞添加於油漆中，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 (Penetrat丨加）和封閉性（sealing)，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。Zinc oxide (Zn) is a widely used metal oxide that can be used in various industries such as plastics, electronic parts, coatings, pharmaceuticals, and cosmetics. · As an important reinforcing agent in the rubber industry, The active agent and Wei' are also the coloring of the self-coloring compound. (IV) The filler has the advantages of improving the purity of the rubber material and resisting the tearing of the limbs. In the printing and dyeing industry, it can also be used as a printing anti-dyeing agent, and can also be used for paints, inks and varnishes. If you add oxidized words to the paint, it will greatly help the mixing of the paint, and you can control the consistency (c〇nsistency), penetration (Penetrat) and sealing. In turn, the film formed by the paint is improved in dryness and chalkiness, reduced in fading and yellowing, and enhanced in resistance to ultraviolet rays and mildew.
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 一種新型的半導體材料，其具有優異的光學與電學特 性，目前已有紫外線探測器、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“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。 4 1377178 然而，具高經濟價值的一維氧化鋅多半是由成本很 高的原生鋅資源直接製得的，但近年來，環保意識提 昇，重視廢料再利用，而煉鋼廢所產生的集塵灰（electric arc furnace dust )廢料就因含有大量的鐵及鋅之化合 物，已成為人們精煉鐵與鋅的重要來源之一；典型的集 塵灰包含氡化鐵、氧化鋅、氧化鉛、氧化鎂、氧化銅、 氧化鈉、氡化鉀等數十種化合物，其中，該集塵灰含量 中的辞與鐵約各佔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鋅。 目前，在國外一般從集塵灰中回收辞的方法均以火 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 :鋅含量可達到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， 使該集塵灰變成辞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辞業與鋅化學製品 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 性’但由於所需投資設備成本較A，且高溫耗損能源多 之因素’需要處理非常大量之粗氧化鋅方可符合成本。 k因此在α備及成本考量上，—般常以濕法進行該粗 錢辞精煉處理方法，参閱圖卜其包含有—備料步驟 11、一單階段浸潰步驟12、淨化步驟13及—結晶步驟 14;其中，該備料步驟心具備有—火法處理後所得之 粗氧化鋅，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辞混合，產生含有硫 酸辞、硫酸鐵以及其他雜質之浸潰液及殘渣於該淨： 步驟13中再利用雙氧水除鐵成分後，以鋅粉去除銅録， 再以高猛酸鉀氧化劑去除猛，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，即完成該粗氧化辞之精煉。 然’前述該粗氧化鋅精煉處理方法1具有下列缺失 產生： 1. 由於該粗氧化辞成分中鐵（G5~1G%)、邪~13%)及氣 (2.5 12%)等雜質含1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〉查内混有有害物質，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 之殘渔，故該殘淺係屬有害事業廢棄物，雖含有大量 之鐵與金。成刀，但因含紐之濕殘渣回收不易故將該 殘渣當廢棄物丢棄時，另需額外進行固化處理，除造 成費用成本高、環境負荷大外，更是鐵、鉛等資源的 浪費。 3.再者，由於該粗氧化鋅中鐵成分中含有難溶性之鋅鐵 尖晶石（ZnFe204)，其必須用大量之強酸液，方能破 壞部分較難溶之鋅鐵尖晶石，故若以單階段式浸漬進 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 量’以達到資源有效利用及環保等功效。 於是，本新型粗氧化鋅精煉處理方法，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’·其巾’該擦洗步财將粗氧化鋅與水進行混 拌’使附著於該等粗氧化鋅表面之含氣鹽類雜質因相互 碰撞溶解而去除，再將該等粗氧化鋅依粒徑大小進行分 選（即分級步驟），以區分出含鐵成分多之重礦及含鉛鋅 成分多之輕礦’最後利用該浸潰步驟中之不同酸鹼值的 硫酸溶液進行浸潰，以分別處理前述分選出不同含量之 粗氡化鋅，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，同時將可使毒性較高之鉛濃集至硫 酸鉛泥中，避免與鐵混合，以達到殘渣量減^外’，'同^ 該殘渣内所含之鐵及㈣分’亦可於該浸潰步驟及後續 1377178 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及結晶般燒步驟37 ;其中，該備料步驟31 係備置附著有雜質之粗氧化鋅，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（40〜65%)、鐵（〇_ 5~10%)、鉛（5 〜13%)、氯（2 5〜15%) 及其他雜質等》 仍續刚述，該擦洗步驟32具備有一可提供強力攪 拌功能之-擦洗機（輯洗機並非本發明之技術特徵， 故不詳述），以將該等粗氧化辞與水以高固體濃度方式 加以混合，且該固液比範圍為1··3~3:1内，而混合後之 漿體以30(Μ_Γ卵間之轉速進行攪拌、擦洗作業以 使附著於該等粗氧化鋅表面之可溶性雜質（如氣化納、 氯化鉀、氯化錯等）可經由授拌過程該等粗氧化辞相互 摩擦碰撞下㈣速轉於水中，藉此除去至少·以上 之H然’為使該擦洗步驟32中之雜質去除效果更 8 1377178 佳，該等粗氧化鋅與水之混拌物中可適時添加有一助拌 物（如氧化鉛或氧化鋁磨球等），而該助拌物之體積約 為漿體之0. 5~1. 5倍。 再者，該分.級步驟33具備有一分級機，該分級機 可以重力分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 中未示出），以便針對前述該擦洗步驟32中所得之該等 粗氧化鋅依粒徑進行分級作業，達到將粗、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 錯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3000〜20000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 鹼值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係利用一酸鹼值0至2之硫酸溶液，以針對含鐵 量高之重礦與著磁輕礦進行浸潰處理，進而破壞該鐵成 9 1377178 分中之辞鐵尖晶石（ZnFe2〇4)，以便將該重礦純化成硫 酸鋅（ZnSCh)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 鋅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鹼值升高之鹼劑（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；另，該鋅粉置換除銅鎘係指利用一鋅粉 加入該硫酸鋅溶液中，使該硫酸鋅溶液中銅及鎘與該辞 粉產生反應而沉澱；至於，該氧化除錳則前述等步驟處 理後之硫酸鋅溶液加入一氧化劑（如高錳酸鉀），以控制 其氧化還原電位ORP在250〜500mV範圍，使該硫酸鋅溶 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），藉此將大部分之錳成分予以去除。 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 化鋅（ZnO)結晶，並提供作為各產業之辞原料；至於， 該硫酸鉛（PbS(h)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 氣及鉛成份去除，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 可提供给煉鋼業者，進入煉鋼製程或鋼廠固雜料回收系 10 统中’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 量高之粗氧化辞進 之工業級氧化鋅，故提出實驗 其採用之粗氧化鋅為電爐煉鋼集塵灰以火法流程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. Characteristics, there are currently zinc oxide semiconductor optoelectronic devices such as ultraviolet detectors, light-emitting diodes and semiconductor lasers, which can be widely used in optical communication "network, photoelectric display, photoelectric storage, photoelectric conversion and photodetection". In other fields, it is known that zinc oxide has become one of the indispensable raw materials in various industries. 4 1377178 However, most of the high-value one-dimensional zinc oxide is directly produced from the costly raw zinc resources. However, in recent years, environmental awareness has increased, and waste recycling has been emphasized. The electric arc furnace dust produced by steelmaking waste has become a refined iron and zinc because of the large amount of iron and zinc compounds. One of the important sources; typical dust collection ash contains dozens of compounds such as antimony iron, zinc oxide, lead oxide, magnesium oxide, copper oxide, sodium oxide and potassium telluride. Among them, the words and iron in the dust ash content account for about 20% wt; therefore, in order to find a way to obtain lower cost, and to make the steel mill waste have better recyclability, people try The use of various methods to recover zinc from dust collection ash. At present, the methods for recovering words from dust collection ash in foreign countries are all carried out by pyrometallurgical method. After the high-carbon carbothermal reduction of dust-collecting ash, the words of high volatility It can be volatilized and concentrated in fly ash. It is called crude oxidation. Its zinc content can reach more than 50%. The technology and equipment used include the Waelz process and the rotary disk furnace method (RHF). And the multi-layer furnace method (MHF); in Taiwan, the steel mills also use the fire method to treat the dust and ash, so that the dust collection ash becomes a crude zinc oxide (Crude ZnO) with high content, and then at a low price. The secondary raw materials are resold to the refining industry and the zinc chemical industry for subsequent refining treatment. Generally, the technology of crude zinc oxide refining can be divided into two major categories: wet and pyrometallurgical; for example, in pyrometallurgy, Different processes such as ISP shaft furnace, electric arc furnace, vertical raft and horizontal raft However, in the application of crude zinc oxide refining, the ISP shaft furnace is the mainstay, and the pyrolysis technology based on carbothermal reduction has high recovery rate and high tolerance to raw material impurities, but due to the required investment equipment cost. Compared with A, and the factor of high temperature consumption and energy consumption, it is necessary to process a very large amount of crude zinc oxide to meet the cost. Therefore, in the case of α preparation and cost consideration, the crude money refining treatment method is often used in the wet method. The drawing includes a preparation step 11, a single-stage impregnation step 12, a purification step 13 and a crystallization step 14; wherein the preparation step has a crude zinc oxide obtained by a fire treatment, the single stage The impregnation step 12 utilizes a strong acid solution (such as sulfuric acid) to mix the crude acid solution with the crude oxidation, thereby producing an impregnation liquid and residue containing sulfuric acid, iron sulfate and other impurities in the net: After removing the iron component from the hydrogen peroxide, the copper powder is removed by the zinc powder, and then removed by the high acid potassium oxidant, and then the mixture is crystallized in the crystallization step , to make the oxidation Mixture is separated, i.e., the completion of the refining of crude oxidation speech. However, the above-mentioned crude zinc oxide refining treatment method 1 has the following defects: 1. Since the coarse oxidized component contains iron (G5~1G%), evil ~13%) and gas (2.512%), the impurities contain 1 equivalent. High, and before the impregnation step, the iron and chlorine are not separated first, and the 'residue generated by the impregnation step> is mixed with harmful substances, which makes the residue difficult to recycle. And even cause environmental pollution. 2. Check that the average treatment of each metric ton of crude zinc oxide will result in a ton of fishing. Therefore, the residual scum is a hazardous business waste, although it contains a large amount of iron and gold. It is a knife, but it is not easy to recycle the residue due to the residue. When the residue is discarded as waste, it needs to be additionally cured. In addition to high cost and environmental load, it is a waste of resources such as iron and lead. . 3. Furthermore, since the iron component of the crude zinc oxide contains insoluble zinc iron spinel (ZnFe204), it is necessary to use a large amount of strong acid liquid to destroy some of the hardly soluble zinc iron spinel, so 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 while increasing the yield of valuable metal by-products and relatively reducing the amount of harmful substances residues. In order to achieve effective use of resources and environmental protection. Therefore, the novel crude zinc oxide refining treatment method comprises a preparation step, a scrubbing step 'grading step, a dipping step and a crystallization calcining step'. The scrubbing step is to mix the coarse zinc oxide with the water. Mixing the gas-containing salt impurities attached to the surface of the coarse zinc oxide by mutual collision and dissolution, and then sorting the coarse zinc oxide according to the particle size (ie, the classification step) to distinguish the iron-containing component The heavy ore and the light ore containing more lead and zinc components are finally impregnated with the different pH values of the sulfuric acid solution in the impregnation step to separately treat the above-mentioned different contents of the crude zinc telluride, in addition to reducing In addition to the use of sulfuric acid in the impregnation step, in order to achieve a reduction in cost, the lead with higher toxicity can be concentrated in the lead sulfate mud to avoid mixing with iron to reduce the amount of residue. The iron and (four) points contained in the residue can also be separated in the impregnation step and the subsequent 1377178 treatment to form a valuable metal recyclate, thereby achieving effective resource utilization 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 crystallizing step 37; wherein the preparation step 31 The crude zinc oxide to which the impurities are attached is prepared, that is, the crude oxidation word in the embodiment can be obtained after the dust collection ash produced by the steelmaking process, for example, the product obtained by the carbothermal dust collection method by the carbothermal reduction method. The composition of the ingredients varies slightly depending on the manufacturer's treatment. The average composition contains zinc (40~65%), iron (〇_5~10%), lead (5~13%), and chlorine (25). ~15%) and other impurities, etc., as described above, the scrubbing step 32 is provided with a scrubbing machine capable of providing a strong stirring function (the washing machine is not a technical feature of the present invention, so it will not be described in detail) to The crude oxidation is mixed with water in a high solid concentration manner, and the solid-liquid ratio ranges from 1··3 to 3:1, and the mixed slurry is stirred and scrubbed at a speed of 30 (Μ_Γ eggs). Soluble impurities (such as gasified sodium) attached to the surface of the coarse zinc oxide Potassium, chlorination, etc.) can be transferred to the water by frictional collision with the coarse oxidized words through the mixing process, thereby removing at least the above H to make the impurity removal effect in the scrubbing step 32 more 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 Further, the sub-step 33 has a classifier which can be subjected to gravity sorting technology for spiral beneficiation or upflow fluid classification, such as using a spiral concentrator, a fluid classifier or a seismic grading. And the like (not shown), in order to perform the classification operation on the coarse zinc oxide obtained in the scrubbing step 32 according to the particle size, to obtain the preliminary separation of the coarse and fine particles of the coarse zinc oxide. Two major categories, such as heavy iron with high iron content and light mineral with high false zinc content, are selected. Of course, in order to make the particles containing iron component in the light mine more complete separation, the light mine after sorting is selected. A magnetic separation step 34 can be added, and the magnetic The step 34 has a magnetic separator capable of providing a magnetic field strength of 3000 to 20000 Gauss to select a high-iron-containing magnetic light ore and a high-lead non-magnetic light ore for the light ore, and the magnetic property The light ore may be mixed with the heavy ore and enter the impregnation step 35 for treatment. The foregoing impregnation step 35 is divided into a slightly acid impregnation 351 and a strong acid impregnation 352; wherein the micro-mine The acid leaching 351 system uses a sulfuric acid solution having a pH 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 utilize micro The light ore is treated by acid leaching to treat the light ore into a zinc sulfate (ZnS〇4) solution and a lead sulfate (PbS〇4) residue; and the strong acid impregnation 352 system utilizes a pH value. a 0 to 2 sulfuric acid solution for impregnation treatment of heavy iron ore with a high iron content, thereby destroying the iron into a spinel (ZnFe2〇4) of 9 1377178, in order to The heavy ore is purified into a zinc sulfate (ZnSCh) 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 zinc sulphate 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 alkali agents that can increase the acid value (such as slaked lime, crude zinc oxide 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 zinc powder to the zinc sulfate solution to make copper and cadmium in the zinc sulfate solution Precipitating with the pulverized powder to form a precipitate; as for the oxidizing and manganese removal, the zinc sulphate solution after the foregoing steps is added to an oxidizing agent (such as potassium permanganate) to control the oxidation-reduction potential ORP in the range of 250 to 500 mV, so that The manganese component of the zinc sulfate solution reacts with the oxidant to produce a precipitate (manganese dioxide solid) whereby most of the manganese component is 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 above step to form zinc oxide (ZnO) crystals, and is provided as a raw material for various industries; The lead sulfate (PbS(h) residue, which can be processed into a lead paste by simple subsequent processing to provide lead or related industries, and the remaining iron-containing residue, due to the steps of washing, grading and magnetic separation Most of the gas 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. The steelmaking process or the steel mill solid waste recovery system is used to recover the iron resources. The following is an experimental grade zinc oxide that confirms that the crude zinc oxide treatment method of the present invention can be used in a large amount. The crude zinc oxide used in it is an electric furnace steelmaking dust collecting ash.
處理後所得之產品，其成分重量百分比如下表所示 d . -般粗氧化辞之鋅含量均15G%以上，本發明特挑 選低品位之粗氧化鋅作為實施案例，以彰顯本發明之特 長）°The weight of the component obtained by the treatment is as shown in the following table. The zinc content of the crude oxidation is 15 G% or more. The present invention selects the low-grade crude zinc oxide as an example to demonstrate the advantages of the present invention. °
Zn Fe Μη Pb Cr Cu Cd Cl 42.09 11.04 0.92 3.23 0.06 0.10 0.28 7.50 以下茲針對每一步驟所得之成果，分析如下· 1.擦洗步驟：Zn Fe Μη Pb Cr Cu Cd Cl 42.09 11.04 0.92 3.23 0.06 0.10 0.28 7.50 The results obtained for each step are as follows: 1. Scrubbing step:
篩分、磁選步驟確實可以將含鐵、鉛 行分離，以及得到高純度 例加以證明 實驗例： 取上述粗氧化辞與清水及助拌物（即氧化銼磨球） 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： 前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 11 1377178 式分級處理可將鐵成份集中之粗顆粒加以選出。 3.磁選步驟： 將分級後所得之輕礦漿體進料至一半連續式濕 式磁選設備中，而被磁場截留之物料為高含鐵之著= 料，出流之礦漿則為高含鉛辞之非著磁料故著礤料 與非著磁料之重量比約為〇.8:1 ;經過採樣分析鐵 總量中有76%集中於著磁料，非著磁料中之鐵含量降 低至3%或更⑯，足見以濕式磁選方式的確可將高含 鐵之鋅鐵尖晶石成分加以分離。 ° 4.浸潰步驟： (a)輕礦處理 tit ^The screening and magnetic separation steps can indeed separate the iron and lead, and obtain high purity examples to prove the experimental example: Take the above crude oxidation and the water and the auxiliary mixture (ie, the cerium oxide ball) at a ratio of 1.1:1. 'At the end, it was rinsed with water, and the chlorine content of the crude zinc oxide obtained was reduced from 7.5 to 1.1%, and the removal rate was as high as 85%. 2. Grading step: After the above scrubbing, after dilution with water, it enters into a spiral concentrator. After grading, the heavy minerals with lighter color and lighter light mines can be obtained. The weight of the heavy ore and light mines The ratio is about 1:2〇; after sampling analysis, the iron content in the heavy ore is increased to 25.8%. It can be seen that the coarse particles with concentrated iron components can be selected by the wet 11 1377178 classification process. 3. Magnetic separation step: The light mineral slurry obtained after classification is fed into a semi-continuous wet magnetic separation device, and the material intercepted by the magnetic field is high iron content = material, and the outflow pulp is high lead word. The weight ratio of the non-magnetic material is about 〇.8:1; after sampling, 76% of the total amount of iron is concentrated on the magnetic material, and the iron content in the non-magnetic material is reduced. Up to 3% or 16 shows that the high iron-containing zinc iron spinel component can be separated by wet magnetic separation. ° 4. Dipping step: (a) Light ore treatment tit ^
輕礦興稀硫酸液混合，招 拌均質化同時並調整邱至4〜45，待授拌至一定與 間後*7漿體以！|當之濾紙H得到殘渣與澄清浴 兩部分；經過採樣分析，澄清液之含量分別為句 92g/卜鐵40〇mg小鋼45mg/1、鍾、勤⑽^The light mine is mixed with dilute sulfuric acid solution, and the homogenization is carried out at the same time and the Qiu to 4~45 is adjusted, and the mixture is to be mixed with a certain amount of *7 slurry to be! |When the filter paper H gets the residue and the clarification bath in two parts; after sampling and analysis, the content of the clarification liquid is respectively 92g/b iron 40〇mg small steel 45mg/1, Zhong, Qin (10)^
而殘渣XRD光譜分析_得大部衫硫酸錯且硫酸 鉛含量為48%。 (b)重礦處理 將步驟2料之重礦及步驟3所得之著磁輕礦愈 硫酸液混合，搜拌均質化同時並調整PH 10 5〜卜 待授拌至-料間後，令㈣以適當之濾紙過遽，得 到殘邊與澄歧_分；_録分析，液體之含量 分別為鋅8〇的、鐵65〇〇mg/i、銅、猛 12 1377178 167mg/l、船4.5mg/l，而殘潰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值升高之鹼劑（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) 鋅粉置換除銅鎘：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鎘之沉澱。 (c) 氧化除錳：於經過a與b處理之溶液加入如高錳酸鉀 之氡化劑，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淨化後之溶液中加入碳酸鈉，且施 以慢速攪拌，以得到白色沉澱物為鹼式碳酸鋅，過濾 13 1377178 後將固體於咼溫環境中進行炮燒，最後可得工業級氧 化辞（經XRD分析結果如圖3所示），故可證本發明確 實能將粗乳化辞處理成南純度之氧化辞結晶。 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，使得該等粗氧化鋅之顆粒 因攪拌下而相互碰撞摩擦，藉以去除大部分附著於該 粗氧化辞表面之可溶性雜質，可將70%以上之氣消 除，使後續上之處理上無氣鹽累積的現象外，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 量咼及含鉛辞量高之粗氧化鋅分離，使該浸潰純化過 程中，只需針對該含鐵量高之粗氧化鋅，進行強酸浸 潰作業，而向含鉛鋅之物料僅須進行微酸浸潰即可達 到/谷出目標，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鋅，以於浸 >貝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 船膏形式作為次級原料之功效產生。 14 1377178 4. 再者，經分級後之重礦與經過磁選的著磁輕礦，其内 部之鉛鋅含量已去除大部份，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、強酸浸漬與純化後所產生之硫酸 φ 錯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 時將可使t性較咼之錯濃集至硫酸錯泥令，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， 而形成有價之金屬回收物，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 ’ 已田不忐以此限定本發明實施之範圍，即大凡依本發 月申專利範圍及發明說明書内容所作之簡單等效變 化與修飾，皆應仍屬本發明專利涵蓋之範圍内。 15 1377178 【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 粗氧化鋅精煉處理方法 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 結晶煅燒步騾 351 微酸浸潰 352 強酸浸潰The XRD spectrum analysis of the residue was obtained by the sulphuric acid and the lead sulfate content was 48%. (b) heavy ore treatment, mixing the heavy ore in step 2 and the magnetic light ore in the step 3, mixing and homogenizing, and adjusting the PH 10 5~b to be mixed into the material, and then (4) After the appropriate filter paper was passed, the residual edge and the singularity were obtained. The liquid content was zinc 8 、, iron 65 〇〇 mg/i, copper, fierce 12 1377178 167 mg/l, boat 4.5 mg. /l, and the residual XRD spectrum analysis measured a small amount of oxides of barium, aluminum, iron, etc., most of which was lead sulfate, and the lead sulfate content was 38%. 5. Purification step: Mix the clear liquid obtained in step 4 into the purification process. The procedure includes: (a) Aeration and iron removal: by adding an alkali agent (such as slaked lime, crude zinc oxide or oxidation) that raises the pH. 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) Displacement of zinc powder in addition to 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, an impurity precipitate can be obtained. The precipitate is mainly precipitated by copper and cadmium. . (c) Oxidation of manganese: A solution 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 purified in step 5, and applying slow stirring to obtain a white precipitate as basic zinc carbonate, filtering 13 1377178 and then spraying the solid in a warm environment. After burning, the industrial grade oxidation word can be obtained (the XRD analysis result is shown in Fig. 3), so it can be proved that the invention can process the crude emulsification word into the oxidized crystal of the southern purity. 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 particles of zinc oxide collide with each other due to agitation, thereby removing most of the soluble impurities attached to the surface of the crude oxidized surface, and more than 70% of the gas can be eliminated, so that there is no accumulation of gas and salt on the subsequent treatment. 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 separation and magnetic separation steps are used to separate the crude zinc oxide with high iron content and high lead content, so that the impregnation purification process only needs to be high for the iron content. Zinc oxide is used for strong acid impregnation, and the material containing lead and zinc only needs to be slightly acid impregnated to reach the target of the grain. In addition to improving the reaction effect, it can reduce the amount of sulfuric acid used and waste acid. Emissions, resulting in lower processing costs, while reducing environmental impact and energy consumption. 3. Continuing with the above, due to the iron oxide and lead-containing raw zinc oxide, the dip > shell step has been previously sorted, so that the lead is concentrated in the lead sulfate mud in the impregnation step 'avoiding iron Mixing with other metals can not only achieve the reduction of harmful sludge, but also provide the effect of using lead sludge as a secondary raw material in the form of ship jelly. 14 1377178 4. Furthermore, after the classification of heavy ore and magnetically selected magnetic light ore, the internal lead and zinc content has been removed, so when the heavy ore and the magnetic light mine are saturated with the strong acid After that, 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 into a steelmaking process or a steel plant solid waste recovery system for iron resources. Recycling. 5, Continued above, the sulfuric acid φ and the iron-containing residue produced by the micro-acid, strong acid impregnation and purification can be separately recovered and utilized separately, so 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, it will make it possible to concentrate the sulphuric acid to the sulphate sulphate and avoid mixing with iron and other less toxic metals to reduce the amount of residue. At the same time, the iron and lead components contained in the residue are also It can be separated in the impregnation step to form a valuable metal recyclate, thereby achieving the effective use of resources and environmental protection, so that the object of the present invention can be achieved. The above description is only for the purpose of illustrating the preferred embodiments of the present invention, and the scope of the present invention is limited by the scope of the invention, that is, the simple equivalent change of the patent scope and the description of the invention according to the present invention. And modifications are still within the scope of the invention. 15 1377178 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a conventional zinc oxide refining process. FIG. 2 is a flow chart of a preferred embodiment of the present invention; and FIG. 3 is an XRD analysis chart of a zinc oxide product produced by the present invention. [Main component symbol description] 3 Crude zinc oxide 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