200904992 九、發明說明： 【發明所屬之技術領域】 本發明係、冑關於一種含銅4金屬肖泥的處王里方法，卢 指-種藉高溫焙燒及硫酸溶液浸潰以將含銅重金屬污炉： 源化’進而製得金屬銅或銅化合物的處理方法。巧泥貝 【先前技術】 煆m子業、印刷電路板業 過中’书會產生大量含有銅、鋅、錫、鐵、鉛、鎳、 銘、鉻等重金屬的廢棄污泥，該含重金屬污泥的妥呈處理 與有效貧源回收再利用為眾廢棄物處理相關業者 力的目標。對於重金屬污泥的處理，除了傳統的固化掩埋 法外’尚有火法冶煉與渔法遞遽的方式。固化掩埋法虽卜 處理重金屬污泥’但處理成本昂f，且未能有 ： 再度利用。 又貝源 火法冶煉係為添加還原劑及冶煉助劑於含重金屬 中，再經乾燥與培燒程序，於高溫下將重金屬化合物2 以製得金屬。火法冶練相關技術係、描述於美國專利公主第 侧763號專利及中華民國公告第彻585號專利中。2 冶煉雖可有效還原重金屬污泥中的有價值金屬化合為 金屬’達到貝源化的目❸’但因重金屬污泥中常含有多種 重金屬之化合物，g]此所得的金屬混合物尚須進—步 還原才能得到純金屬，或摻配其他金屬製成合金。 國=告第503224料利中亦揭露將重金屬之污泥造教、 乾燥、焙燒後，添加其他原料調製成建築或陶瓷用色料。 200904992 然而，由於重金屬污泥的成份複雜，造成焐燒後的重金屬 污泥不易被調製成色料。 溼法瀝濾係利用鹽酸、硫酸、含氣溶液、酸性氯化銅 钱刻廢液等溶液，加入重金屬污泥中將有價值的重金屬化 合物溶解，再以電解、萃取、置換、蒸發結晶等方法回收 製得金屬或其化合物，溼法瀝濾相關技術係描述於美國專 利公告第 4151257、4162294 ' 4242127、4360380 號專利 以及中華民國公告第202419、241247、292274號專利以 及中華民國專利證書號第1228104、1234550、12629〇〇以 及1262901號專利中。但由於重金屬污泥產生過程中常會 添加有機絮凝劑及重金屬捕集劑以加速污泥沈降，及確= 排放水符合環保標準，導致以溼法瀝濾處理重金屬污泥過 程中，形成黏稠狀漿液而非常難以固液分離。本發明人曾 試驗處理多種不同來源的含銅重金屬污泥，於進行溼法= 渡時均會產生黏稠漿液而無法固液分離。 〜 本發明人憑藉多年從事廢棄物處理的經 、佳— 取 積極努力 仃研發，終於提出本發明而可解決 eg 〇 ^ ^笑次瀝濾的問 、，本發明可適用於處理印刷電路板業、電鍍 電子、金屬相關行業所產生的含銅重金屬污泥。，、2 ^他 【發明内容】 有鑑於現有溼法瀝濾技術常會使重金屬污 聚液而吝斗拙r I、，m 成為铜 生難U固液分離的困擾，導致不易回 ::’：發明之目的在於提供一種含銅重金屬污 ’、、係將含銅重金屬污泥高溫炫燒後，再、、“ 6 200904992 以將含銅重金屬污泥資源化，進 %向裂侍金屬銅或銅化合 物。 σ 污泥的處理 污泥氧化焙 為達成以上的目的’本發明之含銅重金屬 方法係包括以下步驟： (a)於500〜1〇〇0。〇之高溫下，將含銅重金屬 燒形成金屬氧化物；以及 (b)將焙燒後之含銅重金屬污泥，以硫酸溶液浸漬溶出 金屬氧化物，形成含酸不溶渣之硫酸銅溶液。 較佳的是，係於600〜800°C之高㈤下收人& 土 、_ 。、同/皿下，將含銅重金屬 污泥氧化焙燒。 較佳的是，浸潰溶出的時間為3〇分鐘至8小時。 較佳的是，將含銅重金屬污泥氧化焙燒10分鐘至 小時。 較佳的是，該硫酸溶液之濃度係為5〜5〇〜％間。 較佳的是，浸潰溶出的溫度為室溫至1 001：間。 本發明由於先將含銅重金屬污泥加以高溫焙燒，以除 去/亏泥中的有機成份，因此焙燒後之含銅重金屬污泥浸潰 至硫酸溶液後，不會形成黏稠漿液而難以固液分離，所形 成的硫酸鋼溶液可輕易與固態之酸不溶渣分離，所以可達 到含銅重金屬污泥的有效資源化處理功效，不僅可避免含 鋼重金屬污泥對環境造成污染，且可回收有價值的銅金屬 或鋼化合物而產生經濟效益。 【貫施方式】 印席】電路板業、電鍍業或其他電子、金屬相關行業所 200904992 產生的含銅重金屬污泥，通當 币5有3〜70wt%的柏人® 氧化銅或氫氧化銅等化合物 鋼金屬（其以 予化口物的形態存在於污 定量的辞、錫、鐵、鉛、鎳、為 匕肀），以及不 " 詞、鋁、鉻等重金屬仆入仏 並多會含有有機絮凝劑與重 ，屬化s物， 至兔屬捕集劑，對於μ 金屬污泥，可使用本發明處 、頒3銅重 理，其係包含以下步驟··方法之較佳實施例加以處 ⑷於則〜刚吖之高溫下’將含銅重 燒，此步驟不僅使含銅重金屬 、’ 比化焙 且使巧泥中的各重金屬化合 刀解 切锝化形成為金屬氧 溫度低於50(TC時，污泥中 备 丁旧有機物不易完全氣化 且氧化分解的速率過慢，若溫 ， 士 4_二τ θ 门、1 Ut)〇 C ’則能源耗用 太大而不具輯性，因此溫度範圍係選在鳩〜屬^ 間，較佳的是，係於6〇〇〜8〇。 、-亏、、尸毫外吐卩A L之同/皿下，將含銅重金屬 5泥乳化焙燒1 〇分鐘至3小時；以及 (b)將培燒後之含銅重全属、、无、、p 金屬气“… 硫酸溶液浸潰溶出 / ，形成含酸不溶渣之硫酸銅溶液；較佳的是， ::酸溶液之濃度係為5〜5〇wt%間，浸潰溶出的溫度為室 1 〇〇 C間’浸潰溶出的時間為3〇分鐘至8小時。由於 金屬污泥經高溫氧化培燒後，其中的有機物幾乎已 完全氧化分解’因此再經硫酸溶液浸潰所形成的含酸不溶 ^之石爪酸銅溶液’極易進行固液分離，而可方便地進行後 二，銅金屬貢源化程序。含酸不溶渣之硫酸銅溶液經過濾 为離後，可得到固態之酸不溶渣與硫酸銅溶液，酸 化去予以處理，而硫酸銅溶液則可藉電解法製得 200904992 以達 金屬銅，或經蒸發濃縮及冷卻处s 到資源化的目地。 ^、，'。曰曰“硫酸麵晶體 下列實施例用於示範說明本發明。 杂a 何方式意欲限制本發明n :Λ〜例不以任 明的材料及方法。 -用於心不如何實施本發 實施例一 取18.0公斤已乾燥之含銅重金屬污泥，内 55.^%、鐵、錫 WH〇4wt%、鎳 〇.〇12wt% 及们.63wt%，於65代高溫下氧化培燒1小時，培燒後 之含銅重金屬污泥f 12.6公斤，内含銅⑴㈣广鐵 2.〇m%、錫 2.38wtQ/。、錳 0.05wt%、鎳 〇 21wt 取5。克培燒後之含銅重金屬污泥，加入/升之二 硫酸溶液，於8(TC之溫度下進行浸潰溶出步驟4小時，之 後進行過濾、水洗及乾燥步驟，分別得到含硫酸銅濾液98〇 毫升、水洗液280毫升與乾渣4.3克，乾渣中含銅 〇.〇94wt%，由此可得知銅的溶出率高達98%，而過程中極 易進行過濾及水洗程序。 實施例二 取20.0公斤已乾燥之含銅重金屬污泥，内含銅 56.9wt%、鐵 〇.76wt%、錫 〇.〇27wt%、錳 〇 〇27wt%、鎳 0_007wt%及鈣1.75wt°/。，於65(TC高溫下氡化培燒i小時， 培燒後之含銅重金屬污泥重14 · 6公斤，内含銅7 〇. 9 w t %、 200904992 鐵1.15wt/0、錫〇 〇57wt%、猛〇·㈣、鎳o.oiw⑼及鈣 2 · 3 0 w t %。 取50.1克焙燒後之含銅重金屬污泥，加入i升之i〇wt% 硫酸溶液’於82〜84°C之溫度下進行浸潰溶出步驟4小時， 之：進行過濾、水洗及乾燥步驟，分別得到含硫酸銅濾液 :升、水洗液940毫升與乾渣3.2 1，乾潰中含銅 〇.3::/。’由此可得知銅的溶出率高於98%，而過程中極易 進行過濾及水洗程序。200904992 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for the treatment of a copper-containing 4 metal shale mud, which is characterized by high temperature roasting and sulfuric acid solution impregnation to contaminate copper-containing heavy metals. Furnace: Catalyst's process for the production of metallic copper or copper compounds. Qiao Mubei [previous technology] 煆m sub-industry, printed circuit board industry in the book will produce a large number of waste sludge containing copper, zinc, tin, iron, lead, nickel, Ming, chromium and other heavy metals, the heavy metal pollution The proper treatment of mud and the recycling of effective lean sources are the targets of the relevant waste disposal industry. For the treatment of heavy metal sludge, in addition to the traditional solidification and burial method, there is still a way of smelting and fishing. Although the solidification burial method treats heavy metal sludge, the treatment cost is high, and it fails to: reuse. In addition, the pyrometallurgical smelting system is a method of adding a reducing agent and a smelting aid to a heavy metal, and then drying and arranging the heavy metal compound 2 at a high temperature to obtain a metal. The related technical department of fire law smelting is described in the patent of the US Patent Princess No. 763 and the Patent of the Republic of China Announcement No. 585. 2 Although smelting can effectively reduce the valuable metal in heavy metal sludge into a metal 'to achieve the goal of shellfishing', but because heavy metal sludge often contains a variety of heavy metal compounds, g] the metal mixture obtained must be further Reduction can be obtained by pure metal or by blending with other metals. Guo = 503, 224, 224, which also discloses that the heavy metal sludge is taught, dried, and calcined, and other raw materials are added to prepare a building or ceramic coloring material. 200904992 However, due to the complex composition of heavy metal sludge, heavy metal sludge after calcination is not easily prepared into a colorant. The wet leaching system uses a solution such as hydrochloric acid, sulfuric acid, a gas-containing solution, an acidic copper chloride, and a waste liquid to be dissolved in a heavy metal sludge to dissolve a valuable heavy metal compound, followed by electrolysis, extraction, displacement, evaporation, and the like. Recycling of metals or their compounds, wet leaching related techniques are described in U.S. Patent Publication Nos. 4,151,257, 4,162,294, 4,242,127, 4,360,380, and the Republic of China Announcement Nos. 202,419, 241,247, 292,274 and the Republic of China Patent No. 1228104 , 1234550, 12629〇〇 and 1262901 patents. However, organic flocculants and heavy metal collectors are often added during the process of heavy metal sludge to accelerate sludge sedimentation, and it is confirmed that the discharged water meets environmental protection standards, resulting in the formation of a viscous slurry during the wet leaching of heavy metal sludge. It is very difficult to separate solid and liquid. The present inventors have experimentally treated a plurality of copper-containing heavy metal sludges of different origins, and when wet method is used, a thick slurry is produced and solid-liquid separation is impossible. ~ The inventor of the present invention has been able to solve the problem of 沥 ^ ^ ^ laughter leaching by virtue of years of research and development of waste treatment, and the present invention is applicable to the processing of printed circuit board industry. Copper-containing heavy metal sludge produced by electroplating electronics and metal related industries. , 2 ^ he [invention] In view of the existing wet leaching technology often makes heavy metal fouling liquid and 吝 拙 r I, m become the trouble of the copper solid difficult U solid-liquid separation, resulting in difficult to return:: ': The purpose of the invention is to provide a copper-containing heavy metal stain, and to heat the copper-containing heavy metal sludge at a high temperature, and then, "6 200904992 to recycle the copper-containing heavy metal sludge into the metal copper or copper. Compound σ sludge treatment sludge oxidative baking to achieve the above objectives 'The copper-containing heavy metal method of the present invention comprises the following steps: (a) at a high temperature of 500 to 1 〇〇 0. Forming a metal oxide; and (b) impregnating the copper-containing heavy metal sludge with a sulfuric acid solution to form a copper sulfate solution containing an acid-insoluble residue. Preferably, it is at 600 to 800 ° C. Preferably, the copper-containing heavy metal sludge is oxidized and calcined. Preferably, the time for the impregnation is from 3 minutes to 8 hours. Preferably, the time is 3 amps to 8 hours. Oxidation of copper-containing heavy metal sludge for 10 minutes to hour Preferably, the concentration of the sulfuric acid solution is between 5 and 5 〇%. Preferably, the temperature of the immersion dissolution is from room temperature to 001: 00. The present invention firstly uses copper-containing heavy metal sludge. High temperature roasting to remove the organic components in the slime. Therefore, after the calcined copper-containing heavy metal sludge is immersed in the sulfuric acid solution, the thick slurry is not formed and it is difficult to separate the solid and liquid. The formed sulfuric acid steel solution can be easily combined with the solid state. The acid-insoluble slag is separated, so that the effective resource treatment effect of the copper-containing heavy metal sludge can be achieved, and the steel-containing heavy metal sludge can be prevented from polluting the environment, and valuable copper metal or steel compounds can be recovered to generate economic benefits. [Practical application method] India] copper-bearing heavy metal sludge produced by circuit board industry, electroplating industry or other electronics and metal related industries, 200,904,992, 3 to 70 wt% of Bairen® copper oxide or copper hydroxide Such as the compound steel metal (which exists in the form of pre-chemical substances in the quantitative quantifier, tin, iron, lead, nickel, and bismuth), and does not have the words, aluminum, chromium and other heavy metals. Containing organic flocculant and heavy, genus s, to the rabbit genus collector, for the μ metal sludge, the invention can be used, 3 copper re-inspection, including the following steps · The preferred embodiment of the method (4) At the high temperature of the concrete, the copper is re-fired. This step not only causes the copper-containing heavy metal, but also the baking of the heavy metal compound in the mud to form a metal oxide with low temperature. At 50 (TC), the old organic matter in the sludge is not easily vaporized and the rate of oxidative decomposition is too slow. If it is warm, the temperature is too large, and the energy consumption is too large. The temperature range is selected between 鸠~属^, preferably, it is between 6〇〇~8〇. 、,,,,,,,,,,,,,,,,,,,,, 5 mud emulsion baking for 1 至 to 3 hours; and (b) copper-containing heavy genus, no, p metal gas "... sulfuric acid solution is leached and dissolved / to form copper sulfate containing acid insoluble slag The solution; preferably, the concentration of the acid solution is between 5 and 5 wt%, and the temperature of the impregnation is room 1 〇〇C. The elution time is 3〇 minutes to 8 hours. Since the metal sludge is oxidized and oxidized by high temperature oxidation, the organic matter is almost completely oxidized and decomposed. Therefore, the acid-insoluble copper salt of the claw acid formed by the leaching of the sulfuric acid solution is extremely easy to perform solid-liquid separation. Conveniently carried out the second, copper metal tribute process. After the solution of the copper sulfate solution containing the acid-insoluble slag is filtered, the solid acid-insoluble slag and the copper sulfate solution can be obtained and acidified to be treated, and the copper sulfate solution can be obtained by electrolysis to obtain the metal copper or the evaporation. Concentrate and cool the s to the resource-oriented destination. ^,,'.硫酸 "Sulphate Surface Crystals The following examples are intended to illustrate the invention. The method of the invention is intended to limit the invention n: Λ ~ examples of materials and methods not to be used. - How to implement the first embodiment of the present invention Take 18.0 kg of dried copper-containing heavy metal sludge, containing 55.%, iron, tin, WH〇4wt%, nickel ruthenium, 〇12wt%, and 63g%, oxidized and simmered for 1 hour at 65 days. The burnt copper-containing heavy metal sludge f 12.6 kg contains copper (1) (four) wide iron 2. 〇m%, tin 2.38wtQ /, manganese 0.05wt%, nickel bismuth 21wt take 5. gram of heavy copper contaminated copper Mud, add / liter of disulfuric acid solution, dip and dissolve the solution at 8 (TC temperature) for 4 hours, then carry out filtration, water washing and drying steps, respectively, obtain 98 ml of copper sulfate-containing filtrate, 280 ml of water washing solution and dry 4.3 grams of slag, dry slag containing copper 〇. 〇 94wt%, from which it can be known that the dissolution rate of copper is as high as 98%, and the process is easy to carry out filtration and water washing procedures. Example 2 takes 20.0 kg of dried copper Heavy metal sludge containing 56.9wt% copper, iron slag. 76wt%, tin bismuth, 〇27wt%, manganese bismuth 27wt%, nickel 0_ 007wt% and calcium 1.75wt ° /., at 65 (TC high temperature, simmering and burning for 1 hour, the copper-bearing heavy metal sludge after the burning is 14 · 6 kg, containing copper 7 〇. 9 wt %, 200904992 iron 1.15wt/0, tin bismuth 57wt%, mammoth·(iv), nickel o.oiw(9) and calcium 2·3 0 wt%. Take 50.1g of copper-containing heavy metal sludge after calcination, add i liter of i〇wt% sulfuric acid The solution was subjected to a dipping and dissolving step at a temperature of 82 to 84 ° C for 4 hours. The filtration, washing with water and drying steps were carried out to obtain a copper sulfate-containing filtrate: liter, a water washing solution of 940 ml and a dry residue of 3.2, and dried. It contains copper bismuth.3::/. 'It can be seen that the dissolution rate of copper is higher than 98%, and the filtration and water washing procedures are very easy in the process.
根據本發明可作之不同修正及變化，對於熟悉該項技 術者而言’顯然不會偏離本發明的範圍與精神。雖然本發 明已敘述特定的較佳具體事實，必須瞭解的是本發明不應 被不當地限制於該等特定具體事實上。事實上，在實施: 發明之已述模式方面，對於熟習該項技術者而言顯而易知 之不同修正亦被涵蓋於下列申請專利範圍之内。 【圖式簡單說明】 益 【主要元件符號說明】 無 10Various modifications and changes may be made to the invention without departing from the scope and spirit of the invention. Although the present invention has been described with particular preferred specific details, it should be understood that the present invention should not be unduly limited to the specific details. In fact, the various modifications that are obvious to those skilled in the art are also covered by the following claims. [Simple description of the diagram] Benefits [Main component symbol description] None 10