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Title 廢鉛蓄電池處理廠廢水中的重金屬去除及回收之技術研究
Abstract 依據環保署的統計，廢鉛蓄電池年回收量約達5萬公噸，經由回收系統回收後再送到處理業處理。處理作業流程係以裁切或粉碎設備，將廢鉛蓄電池予以拆解、破碎分離，再經分選設備回收塑膠碎片及鉛電極板等含鉛物質。鉛電極板等含鉛物質再以熔煉方式處理，生產鉛錠等再生鉛製品。塑膠碎片則賣給塑膠再利用廠製成塑膠粒，成為生產塑膠相關產品的原料。 廢鉛蓄電池處理廠回收鉛都採火法冶金技術，火法冶金設備有空污與耗能等問題，並產出兩大類的含鉛副產品，一種為俗稱的鉛冰料；一種為空污設備的集塵灰，此兩類副產品都含鉛成分，如果要重進爐處理需較高的溫度與能源效率較低。 為解決處理火法冶金技術的缺點，本計畫發展技術浸漬加電解，一方面減少汙泥量，另一方面所得到的鉛再次成為鉛原料再利用，符合廢棄物減量技術以及資源化再利用精神。(一).本研究發現集塵灰(SEM-EDS)成分分析主要元素組成為鉛(Pb)、硫(S)、氧(O)，鉛重量百分比在63-78 wt%之間，鉛含量相當高，具回收與再利用價值。研究處理集塵灰浸漬加電解實驗於鉛濃度(20 g/L)條件下，每產出1公斤鉛需，每公斤成本低於2元。優於業主所提供鉛膏火法冶煉成本每公斤粗鉛3.8元，電解陰極產物鉛純度達99.9%，符合粗鉛品質要求。(二).廢硫酸浸漬集塵灰研究1. 提高固液比可以浸漬出較多鉛離子並有效提高pH值，減少工廠廢水處理液鹼中和廢硫酸水成本。2. A廠最佳固液比操作條件在1.0 (kg/L)。3. 廢酸初始pH高低會對鉛離子漬出量及pH改變造成影響。4. 產出物鑑定為可利用PbSO4成份，如通過一系列反應可生成多種以上的化工產品，如紅丹、黃丹、硝酸鉛、醋酸鉛、鹼式碳酸鉛等，這個硫酸浸漬集塵灰新處理流程成本低且產出價值高。(三).低階鉛冰料浸漬及電解鉛研究目標將鉛冰料的鉛資源化並能將殘餘物無害化，以目前實驗數據20-60%含鉛量估算，每噸鉛冰料可回收200-600公斤鉛，相當於1.2～3.6萬元/噸(鉛價以6萬元/噸計)，如能達污泥無害化可節省每噸1.2萬元有害廢棄物處理費(鉛冰料廠內浸漬及電解處理成本以0.6萬元/噸計)，與之前方法比較淨利益為1.8-4.2萬元/噸，本案例廠業主每月產出10噸低階含鉛冰料，預估每月淨效益為18-42萬元 (暫不估算投資設備成本)。發展浸漬加電解技術，可將集塵灰與鉛冰料資源再生為鉛金屬，轉化率集塵灰為80%以上與鉛冰料50%以上，這項技術與火法冶金比較有初設成本低的優點。
EngTitle Removal and recycling of lead from wastewater of waste lead-acid battery treatment plants
EngAbstract Lead acid batteries are commonly used in the automobiles. The Environmental Protection Administration (EPA) has estimated that about 50,000 tonnes of lead acid battery waste were created every year. Recycling processof lead-acid batteries causes a lot of interest in the issues of the environmental protection.A treatment method is disclosed. The treatment method can recycle lead from air pollution control residues (APCR). In the treatment method, at first, APCR is well mixed with waste sodium hydroxide to release lead ion from APCR. Then, an electrolysis device including at least one cathode and at least one anode is provided for the leachate. Thereafter, an electrolyzing step is performed to use the electrolysis device to electrolyze the leachate so as to reduce the lead ions on the cathode for metal recovery.A hydro-electrometallurgical process to treat with fly ash by leachant and leachate electrolyte on lead recovery was proposed. This study was undertaken to determine the physical and chemical characterization, leaching and electrolysis characteristics of the fly ash, generated by an actual plant and to investigate various leaching agent yield and leachate electrolysis on lead recovery. The fly ash from spent of discarded lead-acid batteries contains mostly lead compound, the main content of A1 sample lead was 66.3%, the particle size distribution of A1 sample 90% was ＜24.8 μm . X-ray powder diffractograms of the fly ash were identification of PbO2.PbO and PbSO4. It can be solubilized with leaching agent, the result being solubility lead that can ultimately be exposed to electrolysis. In order to investigate how [OH−] influences fly ash of leachability , NaOH was used as alkali leaching agent and how [H+] influences fly ash of leachability, HNO3 and CH3COOH were used as leaching agent. The percent of lead leaching yield % in leachate was found between 3.5~69% of fly ash. The parameters considered were the leaching agent concentration, the S/L ratio, and the leaching time under the working circumstances, the optimum conditions was 1.875 M NaOH, S/L ratios of 12, at 8 hour and temperatures 27±3℃, The lead leaching yield % in leachate was found 69% of fly ash. To explore the changes of leachate electrolytic on lead recovery, the anode material and current density and specific energy consumption were also considered during the reaction. The experiments of cathodic Pb and anodic PbO2 electrodeposition, the weight percentage of cathodic Pb and anodic PbO2 for Pb were the range of 22.4~32.1% and 66.0~77.6% during 120 min electrolysis, respectively. We aimed at developing a process using both reactions simultaneously for treating aqueous of Pb2+ from lead–acid battery recycling plants of fly ash. It was new method to treat of fly ash and considered with economic and environmental issue.1. Component analysis of Fly ash by SEM-EDSThe main elements of fly ash are lead (Pb), sulfur (S), oxygen (O), and the lead weight percentage of fly ash is between 63-78 wt%. Fly ash have a high recovery value because of its high lead (Pb) content. From fly ash leaching and electrolysis experiment, we can know that producing of 1 kilograms of lead cost less than 2 dollars at lead concentrations (20 g / L) conditions. This method is better than pyrometallurgy, which is using in factories. The producing of 1 kilograms of lead cost 3.8 dollars by pyrometallurgy. At the end, the method can produce the purity 99.9% of lead on the electrolytic cathode, the purity of lead fits the quality requirements of crude lead.2. The study of fly ash leaching with waste H2SO41. We can increase the pH of waste H2SO4 and the concentrations of lead by increasing the solid-liquid ratio. Because of increasing the pH of waste H2SO4, we can reduce the cost from waste acid-base neutralization.2. The optimum operating conditions is 1 (kg/L).3. The intial pH of waste H2SO4 will affect the leaching concentrations of lead and the magnitude of changes of pH.4. The sludges of leaching experiment is PbSO4 by XRD analysis. It can be produced to many chemical products,such as yellow lead, mineral orange, lead nitrate, lead acetate, basic lead carbonate by a series of reactions. The process is low cost and have high value of products.3. The study of slags leaching and electrolyze leadThe target is reclamation of the lead in slags and the surplus to become innoxious. Accordind to our experiment data, slags contain 20~60 wt% of lead. So 200~600 kg of lead can be reclaim from every ton of slags. It is equivalen to 12~36 thousand NT dollars. If the surplus can be innoxious, we can save 12 thousand NT dollars from every ton of slags. The factory A produces 10 ton of slags every months. We can that there will 180~420 thousand NT dollars of benefit every month.Developing the technique of leaching and electrolysis can reclaim lead from fly ash and slags. The recovery of fly ash and slags is more than 80% and 50%. Compare with pyrometallurgy, this technique has the advantage of low cost of devise in the beginning.
ProjectYear 103
SponsorOrg 基管會
ExecutingOrg 國立成功大學
PublicFullVersionURL http://epq.epa.gov.tw/project/filedownload.aspx?fid=74695