電路板業在製程中會排放含有金屬離子之廢水至廢水處理系統，並以化學混凝技術將金屬離子中和沉澱及混凝濃縮，最後將濃泥經過壓濾即形成本研究所稱之「含重金屬污泥」。該污泥是以水合膠羽物型態存在，容易在酸性環境下被溶解而造成環境危害。根據事業廢棄物管制中心之重金屬污泥統計量發現，90-94年度之發生量約介於23至36萬噸/年，其中又以電路板業及電鍍業產生之含重金屬污泥為主。
本研究就電路板產業生產主流(多層板)進行調查，平均污泥生產因子為1.66 kg/m2，由此推估台灣產出之電路板產業含銅污泥約31,000噸/年。另外供應銅箔給電路板產業之銅箔廠亦會產生類似之污泥，由調查資料得知銅箔廠污泥產生因子約為0.152，由2006年各廠產品數量總和可以推估銅箔廠污泥發生量約為21,000噸/年。另外根據相關研究對電鍍污泥的推估量約為94,000噸/年，因此電路板業及電鍍業每年的污泥量推估約為146,000噸/年。
由於污泥中的金屬物質屬於耗竭性資源，無法由自然界再生，且污泥之銅含量均高於銅礦之可開採品位，屬於值得開發的金屬資源。目前處理污泥資源化之理念係針對污泥中的金屬加以回收，在濕式方法上有酸溶、鹼溶將目的金屬溶出後，純化回收金屬，但是浸漬殘渣往往無法符合TCLP要求，而且過濾也遭遇到脫水問題。在乾式方法上利用大量熱能將污泥中的水分蒸發，達到減溶、減量，提高金屬含量供為冶煉原料，但是也衍生煙塵問題。
由於含重金屬污泥係由廢水中和混凝沉澱所產生，形成高含水率的水合膠羽物，具有金屬種類繁多、成份複雜等特性，與天然礦物具有一定礦物組成、共生礦物固定等性質並不相同。一般無機混凝劑分為Al3+ (PAC或Al2(SO4)3)或Fe3+ (FeCl3或Fe2(SO4)3)兩個系統，污泥大致可以分類為鋁系[Al(OH)3]污泥及鐵系[Fe(OH)3]污泥。而混凝劑及後續步驟添加之高分子凝集劑均用來中和水合膠羽物表面電荷，釋放表面結合水使形成自由水，並且造成水合膠羽物互相靠近而增大粒徑，當施加機械力過濾也無法脫除內部結合水，僅能使污泥含水率下降至75%-80%左右。由於水合膠羽物顆粒微細、結晶特性不明顯、金屬成份複雜且含水率高使金屬含量偏低，無法符合冶鍊業之收料規格，若以現有之資源化技術處理將遭遇經濟效益不足、金屬產品純度不高、過濾脫水問題及浸漬殘渣安定性等問題。
由於污泥特性有異於天然礦物，須另外開發適用於污泥的處理流程，因此本研究以濕式氧化(礦化)方法，使重金屬污泥在水溶液產生礦物相變化，進行礦物性質調整使能夠適合以現有資源化處理技術予以資源化。根據研究結果發現，水溶液銅離子與[OH-]反應生成Cu4SO4(OH)6再轉變為CuO的過程會釋放出H+導致pH下降。由0.01M硫酸銅氧化實驗結果之ORP變化情形，可以了解約40~60分鐘可以生成CuO。當反應溫度提高可以促進CuO的提早生成並有良好的結晶性，且降低濾液之過濾阻抗及降低濾渣含水率。當硫酸銅溶液添加硫酸鋁，[Al]/[Cu]=0.1以上時，對氧化銅結晶相的生成會有影響，當施以加熱時，可以使氧化銅結晶特性明顯，有效改善過濾阻抗及降低含水率至70%左右。而硫酸銅溶液加入亞鐵離子使[Fe]/[Cu]=3以上進行鐵氧磁體化，可以發現鐵氧磁體與氧化銅結晶相，這也顯示可以利用鐵氧磁體與氧化銅不同礦物特性進行分選純化，且經過處理之懸浮液之過濾阻抗獲得改善，亦可將濾渣含水率下降至60%左右。一般壓濾脫水的污泥含水率大多為80%，若能改善污泥特性減少20%的含水率，也就可以使污泥體積減少50%以上。
由於Al(OH)3污泥含有大量之鋁離子，在進行濕式氧化處理的同時，利用鋁的兩性特性將鋁成份移除，而銅可以形成氧化銅留在殘渣中，並改善過濾阻抗及濾渣含水率。有關Fe(OH)3污泥中含有較多之鐵成份，由鐵氧磁體化反應條件得知，含重金屬污泥中的金屬氫氧化物與氫氧化鐵為反應所需之前驅物，若能在污泥鐵氧磁體化反應中補充適當之亞鐵離子，使金屬氫氧化物及鐵離子符合鐵氧磁體之化學計量比(MFe2O4)，則可以將含重金屬污泥予以鐵氧磁體化，而銅成份則以氧化銅晶核形式存在，其餘之重金屬則進入鐵氧磁體結構達到安定化的效果，接著可以利用鐵氧磁體與氧化銅之礦物特性差異予以分離純化，其研究結果分述如下:
Al(OH)3污泥: 2N氫氧氧化鈉浸漬劑浸漬一小時後可以使污泥重量損失達20%。由Arrhenius關係求得反應活化能為9.9 KJ/mol.，顯示該反應受溶解擴散模式所影響，而污泥可溶性鋁鹽容易因為浸漬劑的作用而溶解，這可以鹼浸漬反應達15分鐘，鋁鹽的溶出量即可達54.7%至64.1%。因此除了改善污泥過濾特性，減少濾餅含水率外，並因污泥重量損失，有效達到污泥減容、減量的效果。而鹼浸漬液做為中和劑與混凝劑對模擬廢水具有良好之沉澱分離效果，若能額外添加100 ppm的PAM將能夠有效促進懸浮固粒沉降速度，在5分鐘即使固液界面下降1/2高度。
Fe(OH)3污泥: 污泥經鐵氧磁體反應後能夠生成Fe3O4、CuO、6CuO．Cu2O等礦物相，經由SEM分析發現鐵氧磁體產物係約0.2m之單體所組成之聚合體。該鐵氧磁體產物之選擇性浸漬預備實驗結果發現，當浸漬液pH介於3-4之間，能夠使大部分之氧化銅溶出。但是因為此時H+不足，導致無法使鐵氧磁體的鐵溶出而達到抑制的效果。本研究使用0.5 N硫酸做為浸漬劑，在液固比為5的條件下進行選擇性浸漬實驗，能夠將鐵氧磁體產物中的銅浸出約98%，而鐵的最大溶出量卻僅有0.91%。浸漬殘渣經TCLP試驗檢測發現均符合法規要求。
最後本研究以Al(OH)3系列含銅污泥資源化模組之鹼浸漬試驗，在加熱與曝氣條件下，可溶性鋁鹽的溶出率為87%，而固相殘渣之銅回收率為93%，造成污泥減重為1/3，使污泥達到減量效果。另外由於銅成分被濃縮在固相殘渣中，使得殘渣之乾基銅品位達46.3%，符合冶煉業之金屬品位要求。取聯合廢水處理廠之重金屬廢水以鹼浸漬液進行中和與混凝沉澱，其實驗結果發現當廢水之pH被調整至8時，放流水之金屬離子濃度均小於1 ppm。

The metal-contaminated wastewater produced in the procedure of printed circuit board (PCB) was treated by neutralization and coagulation methods, and the thickened sludge was filtered to form “metal-contaminated sludge” in this study. The sludge was composed of metal hydroxide, and it is easily extracted with acidic solution to hazard the environment. According to the estimation of Industrial Waste Control Center, the metal-contaminated sludge amount was about 230-360 thousand tons per year during the years of 92-94. The PCB and galvanic industries were the major contribution to the sludge production.
The average index of sludge production in double sides of PCB factories was 1.66 kg/m2. According to the ratio of investigated factories revenues and industry revenue in the year of 2003, the annual amount of metal-contaminated sludge was about 31,000 tons. Similarly, the index of sludge production in copper foil factory was 0.152，the conjecture production of sludge was about 21,000 tons according to the yield of copper foil in 2006. Furthermore, the amount of galvanic sludge was estimated to be 94,000 tons by other study. Therefore, the sludge amount of PCB and galvanic industries reached a total of 146.000 tons per year.
Owing to the metal resource of the sludge is an exhausted resource and that could not relive in the nature, therefore, the high grade metal-contaminated sludge is of great worth. The ideas of resource recovery are based on the metal recovery direct from sludge of today. The reagents of acid or alkali were utilized to dissolve the species of various metals and to remove the impurities to recover metal in the hydrometallurgical process, but the residue usually did not meet the standards of TCLP testing and the filtration was also a problem. Although the water content was removed by heat treatment to increase the grade of metal and could be a raw material for pyrometallurgy, but the pollution of flue dust would be derived from the process.
In general, the coagulant of Al3+ (PAC or Al2(SO4)3 or Fe3+(FeCl3 or Fe2(SO4)3) was chosen to utilize in wastewater treatment, and the hydroxide floc of high water content is formed. The various metallic ions are in the floc, and the nature is different from the natural minerals. Therefore, the types metal-contaminated sludge were classified as Al(OH)3 and Fe(OH)3. The coagulant and polymer flocculant were utilized to neutralize the surface charge of hydroxide sediment and the surface water would be released. When the surface charge of hydroxide sediment decrease, the particles would be approached each other to increase the particle size. The inner bound water can not be removed via mechanical means to result in the moisture percentage of sludge is usually 75%-80%. Owing to the sludge characteristics of small particle size, amorphous material, composition complicated and high water content is obvious, it would be not economic to recover resource direct by technologies of hydrometallurgy or pyrometallurgy and the problems of product purity, filtration velocity and residue stabilization would be happened.
Owing to the characteristics of sludge is different from natural resource, it is necessary to develop a method to suit the sludge treatment. Therefore, for improving the mineral characteristics of the sludge, the mineral characteristics of metal-contaminated sludge should be appeared and the contemporary technology is feasible for resource recovery from sludge. According to the results of wet oxidation experiments, the aeration oxidation in the alkaline solution would transform cupric into Cu4SO4(OH)6 if the concentration of [OH-] is not high. If the concentration of [OH-] is enough, the Cu4SO4(OH)6 would be transformed further into CuO. In general, the cupric would be transformed into CuO during 40-60 minutes that could refer the formation to the stable and fixed ORP value. When the temperature of the reaction was increased, the formation of CuO would be promoted and the crystalline characteristic was improved. The moisture content of solid residue was decreased to close to 60%. In general, the moisture content of sludge dehydrated by filtering was 80%. If the filtration characteristics of sludge is improved and the water content could be decreased to 60%, the volume of sludge would be decreased 50%.
When the ratio of [Al]/[Cu] was higher than 0.1, the aluminum content would interfere with the formation of CuO. If the temperature of reaction was increased, the specific filtration resistance value would be decreased and the moisture content of solid residue was also decreased to 70%. Furthermore, the ratio [Fe]/[Cu] was higher than 3 in ferrite process, the phases of ferrite and copper oxide would be found in solid residue. It indicates that the mineral characteristics of ferrite and copper oxide would be utilized to recover the valuable metal in the ferrite complex. The specific filtration resistance value would be decreased and the moisture content of solid residue was also decreased to 60%. Owing to the Al(OH)3 sludge contained great amount of aluminum content, the utilizations of amphoteric characteristic of aluminum content and aeration oxidation in this study expect that the Al3+ could be removed and the valuable material was concentrated in the residue. Another type sludge (i.e., Fe(OH)3) contained great amount of Fe3+ and hydroxide that are the precursors of ferrite process, and additional ferrous was added calculated dosage to form the ferrite. The metals except copper content of copper-contaminated sludge would be incorporated into ferrite structure, and the CuO would be formed and maintained in the ferrite complex. The different mineral characteristics of ferrite and CuO could be utilized to recover the copper from the ferrite complex. The relative results are explained as followed:
Al(OH)3 sludge: The weight loss of sludge was 20% when the sludge was leached with alkaline reagent (i.e., 2N NaOH) in one hour. The dissolution of soluble content of the sludge was easily completed in the alkaline leaching process because the activity energy was 9.9 KJ/mole. which calculated from Arrhenius plot and that was controlled by dissolution-diffusion model. The dissolution rate of alkaline leaching could be proved by the dissolution percentage was 54.7%-64.1% in 15 minutes. The reduction of water and solid content in sludge would make the sludge volume decrease greatly. The alkaline leachate was utilized to neutralize the synthetic wastewater, and the sediment settling was satisfied the operation requirement. The settling would be promoted the interface to drop to the half of beginning height in 15 minutes if the 100 ppm PAM was utilized in the suspension.
Fe(OH)3 sludge: The ferrite complex could be formed from metal-contaminated sludge in the ferrite process and the mineral patterns were Fe3O4, CuO, 6CuOCu2O. The SEM images could prove that ferrite complex was composed of many 0.2 m particles and they aggregated densely. In preliminary selective leaching process, the dissolution of CuO would be promoted and that of iron repressed when the leachate pH was controlled at 3-4. In larger scale (i.e., 40 grams ferrite complex) selective leaching process, the 0.5 N H2SO4 and the (leachant volume)/(ferrite complex weight) ratio of 5 were chosen, and the dissolution percentages of copper and iron were about 98% and 0.91% respectively. The leached residue was tested by TCLP, and requirement of regulation standards were met.
Finally, the Al(OH)3 sludge was chosen for the operation of alkaline leaching process on a pilot plant scale, the dissolution of aluminum and recovery of copper were 87% and 93% respectively. The weight loss of sludge was 24% that makes the waste reduction and the copper was concentrated in leached residue to meet the requirement of copper pyrometallurgy. The alkaline leachate was utilized to neutralize the wastewater of united wastewater treatment system, the regulation requirement of effluent would be met when the pH of wastewater was controlled to 8 and the metal concentrations of the effluent were all less 1 ppm.

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