1343363 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】1343363 Nine, invention description: [Technical field to which the invention belongs] This creation belongs to the field of environmental protection and waste resource recycling technology. [Prior Art]
國内印刷電路板業與鋪製造業因於製程中會使用铜原料，故會 衍生出大量之銅污泥，銅污泥中含有大量的銅金屬資源，具有資源回 收之價值。目前國内對於銅污泥之處理技術大致上可以區分為安—固 化 '高溫冶煉（氧化、還原、揮發冶煉）、濕法冶金（酸驗浸漬、固液 分離、純化、回收）' 微生物處理（濃縮、分離、堆肥）等方式。其中 將銅污泥以高溫方式進行熱處理，需消耗相纽大之能源，^大幅增 加了處理成本，而微生喊理;JT式财财狱域㈣固化安定 方式又必將產生更大量之廢棄物與棄置等問題。故本發明將以濕法冶 金方法來回收銅污泥。 經查國内相_污泥資源回收之專利，如中華民國專利編號 国·含銅污泥回收氧化銅之方法(_)」及中華民國專利編號 1262901 「含銅污泥回魏摘之綠㈡」，如容主魏縣船泥置於硫 k液中進仃韻，浸潰後進行隨分離進喊得—含銅之酸浸潰液， 再利用㈣練及雜礬技織氨歸處㈣制氧倾，該兩種方 法於得到氧化銅後皆有廢水產生，且皆會產生絲而需後續安定固化 處理；中華關專機號123侧「含缩泥之連續浸潰喊法」，其 7Domestic printed circuit board industry and shop manufacturing industry will use copper raw materials in the process, so a large amount of copper sludge will be derived. The copper sludge contains a large amount of copper metal resources, which has the value of resource recovery. At present, domestic treatment technology for copper sludge can be roughly divided into an-curing 'high temperature smelting (oxidation, reduction, volatile smelting), hydrometallurgy (acid immersion, solid-liquid separation, purification, recovery)' microbial treatment ( Concentration, separation, composting, etc. Among them, the copper sludge is heat-treated at a high temperature, which consumes the energy of the phase, and greatly increases the processing cost, and the micro-career; the JT-style financial domain (4) curing and stability will inevitably generate a larger amount of waste. Problems such as objects and disposal. Therefore, the present invention will recover copper sludge by a wet metallurgy method. The domestic phase _ sludge resource recycling patent, such as the Republic of China patent number country · copper-containing sludge recovery copper oxide method (_)" and the Republic of China patent number 1262901 "copper-containing sludge back to the green pick (2) "If Rongrong Weixian ship mud is placed in the sulfur k liquid into the rhyme, after the impregnation, it will be shouted with the separation - copper acid soaking liquid, and then use (four) practice and miscellaneous techniques to weave ammonia (4) In the two methods, after the copper oxide is obtained, there is waste water, and both of them will produce silk and need to be stabilized and cured. The Chinese side of the special machine No. 123 side "continuous impregnation method with shrinkage mud", 7
1343363 内谷主要係將含銅污泥經由硫酸及雙氧水混合液逆向方式連續浸漬 後，將所得浸潰液利用氨水調整pH值氨浸後，再進行固液分離，得到 氨銅溶液後進行蒸氨程序即可獲得氧化銅且可回收氨氣再利用，但仍 產生殘渣而需後續安定固化處理。 細合上述結果得知，並未發現國内有任何相關專利與技術可利用 鋼污泥為補來進行資源·，以獲得硫酸銅晶體、銅誠品與硫酸 亞鐵《彳產rm ’並且可達成銅污泥「零廢棄」資源回收與銅資源百分之 百完全資源化之目標。故本發明可提供_相關f者作為資源回收銅 污泥之依據。 【發明内容】 國内印刷電路板業所產生的含銅污泥其含銅量約為15〜17%，另銅 洛製造業巾職生的含銅污·丨朗含21〜27%之銅，這些銅污泥中的 銅金屬品位’遠超過天油割採品㈣下限（銅：0.5% )，故銅污泥 之貝源化回收利益是相#高’甚具回收價值，如無法將這些銅污泥予 以回收再_ ’將會造祕體社會f源之浪f，甚為可惜。 ;銅污泥主要疋以難洛之氫氡化合物存在，若是在強酸或強驗環 境下’氫氧化鋼為主要優勢物_穩定性將受到破壞，因而可利用硫 酸浸潰與晶析法來析_場價值之硫酸銅（CuS〇4 . _晶體， 硫酸銅—朗料綱添加劑、含鋼錢祕、養錄業用殺菌劑或 印染觸解；翻職粉置換法來置換出金屬銅（〇0粉，其含銅 8 量 > » ... t Λ _· »»私‘· · I — — ! 约在61〜99%之卩卩， 可作為銅冶煉廠之冶煉原料。另外硫酸亞鐵 (FeS04 * 5H20 4/ Ρρ^η -7ΤΤ ^ υ4 7Η2〇) ’俗稱綠礬、外觀為藍綠色結晶顆粒， 途為飼料添加劑'土壤改良藥劑、廢水處理之凝聚劑及電路板 蝕刻液等。 σ上述本發明乃針對銅污泥中之銅有價金屬進行資源回收工 本發月内4主要是先將含銅污泥巾加人濃硫酸與去軒水予以完 王/又凊讀後’崎得高濃度娜子之浸潰液再騎得之浸漬液於 至皿下進行靜置晶析步驟，靜置晶析完成紐由過濾即可獲得具市場 ^值之RJ、.’屯度钱銅晶體產品，而其過紐之晶析殘留液之中仍有少 里之銅離子，再將此晶析殘留液中放人鐵粉予以進行置換將鐵粉置 換後所得之置換溶液進行過濾，即分_得可_之固體銅粉產品與 可作為廢水凝聚劑之液體硫酸亞鐵副產品。 銅泥經本發明之資源喊綠處錢，可獲得顧銅晶體、銅粉 產品及硫酸亞綱產品可提翻關產#，不僅可達細污泥中铜 資源百分之百完全資源化之目的’減少銅資源的浪費，並且本方法於 資源回收處理過成中完全不會產生任何衍生廢棄物，為一套「零廢棄 之銅污泥資源回收處理流程。 【實施方式】 本發明之較佳方法示於第一圖，首先將收集之銅污泥1 (其外觀如 第二圖所示，且經由金屬全含量測定得知所收集之銅污泥其鋼含量約 1343363 正1 為Μ〜27% )，進行浸潰雜2步驟，此浸潰祕2步驟之操作條件為： 銅污泥添加量=5公克’去離子水添加量=丨5毫升，麵硫酸=1.2毫升， 浸潰溫度=70°C，浸潰時間=4小時及娜轉速=15〇_。經浸潰溶姓2 步驟之後’可將污泥巾之銅熟他金屬溶解於減巾絲浸潰液2】， 再將浸潰液21進行靜置晶析3步驟，此靜置晶析3步驟之操作條件為: 靜置時間=15小時及靜置溫度=坑。待靜置晶析3步驟完成後將所 得之靜置晶析溶液31進行過.步驟，以將靜置晶析3後所生成之固 體42與晶贼留液4〗相錄，而分離後所得之_42即為高純度 之藍色硫酸銅晶體產品43 (其外觀如第三圖所示）。 另晶析殘留液41中尚含銅離子，爲回收所有有價銅資源，再將晶 析殘留液41進行置換5步驟，以將晶析殘留液41中銅離子予以完全 回收，此置換5步驟之操作條件為：置換時間=2小時、置換溫度=2代 及置換劑=鐵粉或鐵片。經置換5步驟後，由於銅與鐵會產生置換反應， 晶析殘留液4丨巾所含之娜子將會被鐵金屬置換絲，經置換5步驟 後所得之置換溶液61經猶7步驟後，可將置換6後所生成之固體幻 與液體61分離，過慮7步驟分離後所得之固體⑺即為金屬鋼粉產品 63 (其外觀如第四圖所示），其銅金屬之置換回收率可達mo%。 另過渡7步驟分離後所得之液體Μ即為硫酸亞鐵副產品7 (其外 觀如第五_示），此魏亞鐵副產品7可作為廢水處理單元中之凝聚 劑，根據本發明實際以懸浮固體（S.S·)濃度約為500mg/L之原始廢水 測私知’於H)毫升原始廢水中添加〇.丨毫升之硫酸亞鐵副產品7， 10 13433631343363 In the inner valley, the copper-containing sludge is continuously impregnated in a reverse manner through a mixture of sulfuric acid and hydrogen peroxide, and the obtained impregnation liquid is adjusted to pH ammonia ammonia by ammonia water, and then subjected to solid-liquid separation to obtain an ammonia copper solution and then steamed ammonia. The program can obtain copper oxide and can recover the ammonia gas for reuse, but still produces residue and needs to be stabilized and cured. Based on the above results, it has not been found that there are any related patents and technologies in the country that can use steel sludge as a supplement to carry out resources to obtain copper sulfate crystals, copper Eslite and ferrous sulfate. Achieve the goal of “zero waste” resource recovery of copper sludge and 100% complete recycling of copper resources. Therefore, the present invention can provide the basis for the recovery of copper sludge as a resource. [Summary of the Invention] The copper-containing sludge produced by the domestic printed circuit board industry has a copper content of about 15 to 17%, and the copper-containing sewage of the Tongluo manufacturing industry has a copper content of 21 to 27%. The copper metal grade in these copper sludges is far beyond the lower limit of the oil-cutting products (4) (copper: 0.5%), so the benefit of the copper-based sludge recovery is that the phase #高' has a recycling value, such as It is a pity that these copper sludges will be recycled and reused. Copper sludge mainly exists in the presence of dysprosium hydroquinone compounds. If it is in a strong acid or strong environment, 'hydrogenated steel is the main advantage _ stability will be destroyed, so it can be analyzed by sulfuric acid leaching and crystallization method. _ field value of copper sulphate (CuS 〇 4 . _ crystal, copper sulphate - lang material additive, containing steel money secret, breeding industry fungicide or printing and dyeing touch; replacement powder replacement method to replace metal copper (〇 0 powder, which contains 8 kinds of copper > » ... t Λ _· »»私 '· · I — — ! After about 61~99%, it can be used as a raw material for smelting in copper smelters. Iron (FeS04 * 5H20 4 / Ρρ^η -7ΤΤ ^ υ4 7Η2〇) 'Commonly known as green 矾, the appearance of blue-green crystalline particles, the way for feed additives 'soil improvement chemicals, wastewater treatment coagulant and circuit board etching solution. σ The above invention is for the recovery of copper valuable metals in copper sludge. The main reason is that the copper-containing sludge towel is added with concentrated sulfuric acid and de-xuan water to complete the king/re-study. The high-concentration Nazi's immersion liquid is then immersed in the immersion liquid for the stationary crystallization step. After the crystallization is completed, the RJ, . '屯 钱 铜 copper crystal product with market value can be obtained by filtration, and there is still a small amount of copper ions in the crystallization residue of the nucleus, and then the crystallization is performed. The iron powder is placed in the residual liquid to be replaced, and the replacement solution obtained by replacing the iron powder is filtered, that is, the solid copper powder product which is divided into a liquid and a liquid ferrous sulfate by-product which can be used as a wastewater flocculating agent. The resource shouts green money, and can obtain the copper crystal, the copper powder product and the sulfuric acid sub-products can be turned over and over. #, not only can achieve the goal of 100% complete utilization of copper resources in the fine sludge, reducing the waste of copper resources. Moreover, the method does not generate any derivative waste in the process of resource recovery and treatment, and is a set of "zero waste copper sludge resource recovery processing flow." Embodiments The preferred method of the present invention is shown in the first figure. Firstly, the collected copper sludge 1 (the appearance is as shown in the second figure, and the copper content of the collected copper sludge is about 1343363 positive 1 is Μ~27%), and the impregnation is performed. 2 steps, this dipping secret 2 The operating conditions are as follows: Copper sludge addition amount = 5 grams 'Deionized water addition amount = 丨 5 ml, surface sulfuric acid = 1.2 ml, impregnation temperature = 70 ° C, impregnation time = 4 hours and Na rpm = 15 〇 _. After immersing in the surname 2 step, 'the copper of the sludge towel can be dissolved in the metal wire soaking solution 2】, and then the immersion liquid 21 is subjected to static crystallization 3 steps, which is allowed to stand. The operating conditions of the crystallization 3 step are: standing time = 15 hours and standing temperature = pit. After the step of standing crystallization 3 is completed, the obtained standing crystallization solution 31 is subjected to a step to stand still. The solid 42 formed after the analysis 3 is recorded with the crystal squid 4, and the _42 obtained after the separation is a high-purity blue copper sulfate crystal product 43 (the appearance is as shown in the third figure). Further, the crystallization residue 41 contains copper ions, and in order to recover all the valuable copper resources, the crystallization residual liquid 41 is replaced by 5 steps to completely recover the copper ions in the crystallization residual liquid 41, and the replacement is performed in 5 steps. Operating conditions are: replacement time = 2 hours, displacement temperature = 2 generations and displacer = iron powder or iron tablets. After the substitution of 5 steps, the copper and iron will undergo a displacement reaction, and the crystallization of the residual liquid 4 will be replaced by the iron metal, and the replacement solution 61 obtained after the replacement of 5 steps will be followed by the step 7 The solid phantom formed after the replacement of 6 can be separated from the liquid 61, and the solid obtained after the separation in 7 steps (7) is the metal steel powder product 63 (the appearance is as shown in the fourth figure), and the replacement yield of the copper metal is replaced. Up to mo%. In addition, the liquid hydrazine obtained after the separation in 7 steps is ferrous sulfate by-product 7 (the appearance is as shown in the fifth figure), and the Wei yarn by-product 7 can be used as a coagulant in the wastewater treatment unit, according to the present invention, actually suspended solids (SS ·) The original wastewater of a concentration of about 500mg / L is measured in the 'in H' milliliters of raw wastewater added 〇. 丨 ml of ferrous sulfate by-products 7, 10 1343363
可達到最佳之廢水混凝效果’其混凝後(s.s.)濃 度約降低92%，第六圖為10毫升原始廢水經添加不同體積之硫酸亞鐵 副產品7混凝後廢水澄清液中之懸浮固體（s.s.)濃度測定結果。 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. 本發明可回收銅污泥之有價銅金屬，減少銅資源之浪費。 2. 本發明之技術絲可獲得具市場銷售價值之「硫義晶體」產 品、「銅粉」產品及「硫酸亞鐵」副產品，且達到銅污泥中銅 金屬百分之百完全資源化之目標。 3. 本發明於資源回收處理過成中完全不會產生任何衍生廢棄 物，可達到「零廢棄」銅污泥資源回收之目的。 4. 本發明可避免銅污泥污染環境。 5. 本發明可提升國内銅污泥整體之資源再生效益。 6. 本發明具安全性與進步性。 7. 本發明具工商界與產業界之利用價值。 综上所述，本發明誠已符合㈣專利之巾請要件，並依法提出申 祈請鈞局審查委員明鐘，並賜予本發明專利權，實感德便。 【圖式簡單說明】 第一 2)淥本發明「銅污泥資源回收之方法」之實施苄浐圖 第二圖係本發明所使用之銅污泥外觀照片。 1343363 丨恥飞:蘇每正 %月曰， 第三圖係本發明所製備出之高純度硫酸銅晶體產品之外觀照片。 第四圖係本發明所製備出之金屬銅粉產品之外觀照片。 第五圖係本發明所製備出之硫酸亞鐵副產品之外觀照片。 第六圖係硫酸亞鐵副產品混凝後廢水澄清液中之懸浮固體（s.s.)濃度 測定結果。 【主要元件符號說明】The best wastewater coagulation effect can be achieved. The concentration of ss after coagulation is reduced by about 92%. The sixth figure shows the suspension of 10 ml of raw wastewater by adding different volumes of ferrous sulfate by-product 7 after coagulation. Solid (ss) concentration measurement results. In order to make the present invention more expressive and practical, the advantages of the present invention are as follows: 1. The present invention can recover the valuable copper metal of copper sludge and reduce the waste of copper resources. 2. The technical yarn of the present invention can obtain a "sulphur crystal" product having a market value, a "copper powder" product, and a "ferrous sulfate" by-product, and achieve the goal of 100% complete recycling of copper metal in copper sludge. 3. The invention does not generate any derivatized wastes in the process of resource recovery and treatment, and can achieve the purpose of "zero waste" copper sludge resource recovery. 4. The invention can avoid copper sludge polluting the environment. 5. The invention can improve the resource recycling efficiency of the domestic copper sludge as a whole. 6. The invention is safe and progressive. 7. The invention has the use value of the business community and the industry. In summary, the present invention has been in compliance with the requirements of the (4) patent towel, and has filed a lawsuit in accordance with the law, requesting the examination committee member Ming Zhong, and granting the patent right of the invention. BRIEF DESCRIPTION OF THE DRAWINGS First, the second embodiment of the present invention is a photograph of the appearance of a copper sludge used in the present invention. 1343363 丨影飞: Su is positive % 曰, the third picture is the appearance of the high-purity copper sulphate crystal product prepared by the present invention. The fourth figure is a photograph of the appearance of the metal copper powder product prepared by the present invention. The fifth drawing is a photograph of the appearance of the ferrous sulfate by-product prepared by the present invention. The sixth figure shows the concentration of suspended solids (s.s.) in the wastewater clearing solution after coagulation of the ferrous sulfate by-product. [Main component symbol description]