* 高濃度含銅廢水資材化處理技術之探討 Reclaiming Useful Materials from High Copper Containing Wastewater by Magnetic Separation * 1 1 2 3 J. Y. Wu 1 W. S. Chen 1 Y. H. Shen 2 M. S. Tsai 3 ph ph TCLP ( ) 關鍵詞 : The purpose of this treatment process is to provide a reclaiming method for treating high copper concentration wastewater. In the first stage of mineralization, the wastewater is added into a tank with sodium hydroxide solution followed by the addition of Fe 3+ ion and heated to 70. The molar ratio between Fe 3+ and Mt 2+ ion is maintained and the ph value of solution is controlled in a strongly alkaline environment. In the inverse mixing method (adding high copper containing wastewater to sodium hydroxide solution), the precipitation process was carried out in an alkaline solution with ph value greater than 12.5, which resulted in simultaneous precipitation of Fe 3+, Cu 2+, Ni 2+ and Zn 2+ ions. The reaction of the first stage is complete when the ORP reading remains constant. In the second stage of magnetization reaction, the formation of magnetic ferrite, Fe 2+ ion is added to the solution accompanied while being heated and aerated. Magnetic separation is used for the solid-liquid separation. Results show that the concentration of copper and heavy mineral ions of the effluent is well below the regulatory standards and the solid products meet the TCLP test standards of EPA. The solid products are magnetic and have the characteristic of evenly distributed copper ions, which can be recycled and applied as pigments, catalysts and adsorbents for exhausted gases. Key words: m at e r ializat ion, h ig h copper cont ai n i ng wastewater, mineralization, magnetization, magnetic material 壹 前言 96 A 13.33.7 6.1 C 5.6 1. 2. 3. 1.Ph. D. student, Department of Resources Engineering, National Cheng Kung University and Research Assistant, Resource Recycling and Management Research Center, 2.Professor, Department of Resources Engineering, 3. Honorary Professor, Department of Resources Engineering, Chairman, the Formosa Association of Resource Recycling, National Cheng Kung University -75-
8 D 70.7 66 1.1 1,144 108.5 31,000 21,000 94,000 146,000 (1) (2,3) (PAC) (FeSO 4 ) ph 2 3 ph 6 9-1 (cksp) ph (1) Cu(OH) 2(S) D Cu 2 2OH --------------------------(1) K 10 20.4-1 (cksp) ph polymer -2 TCLP -3 (4~11) (2) (3) 100 mg/l -76- 九十八年六月
ph 2 3 ph 10.0 (CuO) Fe(OH) 2 Fe(OH) 2 CuO Jahn-Teller Fe(OH) 2 H 2 O (6) -3 TCLP TCLP XM 2 (3 X)Fe 2 60H M x Fe 3 x (OH) 6 (2) M x Fe 3 x (OH) 6 1/2O 2 M x Fe 3 x O 4 3H 2 O (3) 貳 含銅廢水處理技術之文獻彙整 -1 (12~20) TCLP (21~24) -1 No // 1 (12) 利用超音波與電化學法處理螯合性含銅廢水 2 ph ph3>ph>5>ph>7 ph3 EDTA H + H 4 EDTA H 3 EDTA EDTA 2>1.0>0.5 V/cm -77-
2 (13) 3 (14) 4 (15) 5 (16) 6 (17) 7 (18) 8 (19) 9 (20) 電解和離子交換法回收含銅廢液及污泥中的銅金屬 2 Utilization of spent copper-pickle liquor for recovery of metal values Renewable Energy 23 (2001) pp.651-662 M.H.H. Mahmoud 2 Copper and nickel recovery from acidic polymetallic aqueous solutions Minerals Engineering 20 (2007) pp.753-760 I. Giannopoulou 2 Role of various parameters in synthesis of in soluble agrobased xanthates for removal of copper from wastewater Bioresource Technology 97 (2006) pp.2407-2413 Saswati Chakraborty 2 Copper removal from effluents by various separation techniques Hydrometallurgy 74 (2004) pp.149-156 N.k. Lazaridis 4 Metal recovery from a copper mine effluent by a hybrid process Chemical Engineering and Processing 47 (2008) pp.596-602 V. Nenov 5 Use of RO and NF for treatment of copper containing wastewater in combination with flotation Desalination 221 (2008) pp.2407-2413 P.S. Sudilovskiy 3 Cementation of Copper on Aluminum in Alkaline-Solutions Journal of the Electrochemical Society 143 (1996) pp.1300-1305 Djokic 2 ph 1 8A 24hr >99.9% TP207 3 94.3%COD 35g/L 25g/L1.1g/L 10% Acorga5640 ph 2 10 O/A 43M /ph 7.6pH 9.0 chalcopyrite(cufes 2 ) 16CMD 1// / 2IBX IWX NaOH KOH IBX IWX 26.9 mg/g 27.8 mg/g 3 (1) (2) Cu(OH) 2 (3)(Zeolite) 10 /USD 1.15 USD1.76 USD 68.8 / Fe(OH) 3 ph>4cu(ooh) 2 ph>6.5 RO /NF ph=9.5 7 8ppm SDS(sodium dodecyl sulfate 1.5~2ppm PAA poly acryl amide rejection >99% Cu2+ 0.637~3.57g/LpH 11~14 ph -78- 九十八年六月
參 處理技術與流程說明 3.1 處理技術 100~24,000mg/ L ph TCLP ph -2-3 -2 (1) 24,000mg/L 12,000 2,000 (2) TCLP (3) (4) H 2 S NOx SOx 3.2 處理流程 ph -79-
ph 12.5 FeCl 3 Fe 2 (SO 4 ) 3 Fe(NO 3 ) 3 Fe 2 (CO 3 ) 3 2 ph 12.5 Cu(OH) 3 Cu(OH) 2 4-2 60 90 FeCl 2 FeSO 4 Fe(NO 3 ) 2 FeCO 3 2 ph10.0 60 904 Liter air/ min/liter liquid 3 mg/l TCLP 15 mg/l 2pH -3-4 (1) AW1 BpHD1( ph 12.5 GpH 12.5-80- 九十八年六月
(2) ph W2C 2 phd2 ph 12.5 F6090 ORPE GORP 0.5~2 (3) C 2 phd2 ph 10.0 F6090 H 4 Liter air/min/liter liquid ORPE GORP ph< 8.0 NaOH 1. Fe 3+ /Cu 2+ = 2 2. = 80 C 3. = 400rpm 4. ph>12.5 1.Fe 2+ /Cu 2+ = 2 2.= 80 C 3.= 400rpm 4.pH>10.0 5. =4L air/min/l liquid ( ) XRD -3 D1 NaOH Fe 2+ Fe 3+ NaOH D2 E F W3 G W1 W2 A B C 1 H J R P N K2 M K1 L -4-81-
0.5~2 (4) W3 J K1 LpH -5XRD M K2 LN105 P RJCPDS Joint Committee On Powder. Diffraction Standard XRD -5Cu-ferrite CuFe 2 O 4 A B C D1 D2pH E ORP F G H J K1 K2 L M N P W1 W2 W3 肆 處理結果 4.1 模擬重金屬廢水處理結果 4600~24,000 mg/l -2-3 -2 ph 9.0-82- 九十八年六月
-3 TCLP TCLP -2 :mg/l No. ph 600mg/L 600 100 200 100 3.06 1 0.19 0.17 0.11 0.08 7.84 0.26 0.11 0.13 0.16 10.52 0.16 0.12 0.10 0.13 10.77 2,000mg/L 2,000 100 200 100 3.07 2 0.13 0.21 0.21 0.15 8.12 0.29 0.08 0.17 0.10 10.74 0.32 0.15 0.19 0.07 9.94 6,000mg/L 6,000 100 200 100 2.95 3 0.21 0.16 0.15 0.14 7.88 0.15 0.23 0.13 0.05 10.48 0.40 0.13 0.22 0.18 10.61 24,000mg/L 24,000 100 200 100 3.02 4 0.27 0.14 0.04 0.24 7.97 0.21 0.09 0.18 0.20 10.79 0.31 0.17 0.17 0.16 10.42 3.0 2.0 1.0 5.0 6.0~9.0-3 TCLP :mg/l No. 1 ( 600mg/L) 2 ( 2,000mg/L) 3 ( 6,000mg/L) 4 ( 24,000mg/L) 124.5 25.3 35.7 24.9 78.6 1.5 1.1 0.6 2.5 1.3 0.7 0.8 178.8 135.8 67.9 15.6 217.2 2.4 0.6 0.7 4.8 1.9 0.8 1.1 875.3 389.4 42.77 11.5 647.2 1.2 0.37 0.3 6.1 1.3 0.81 0.6 978.1 798.3 58.99 17.6 1,145.5 1.9 1.01 0.7 6.7 1.2 0.93 1.2 TCLP 15.0 5.0-83-
4.2 實際電鍍廢水處理結果 ( ) -4 TCLP-5-4 5TCLP TCLP -4 :mg/l No. 1,589 355 489 12 61 383 1 0.15 0.21 0.05 N.D. 0.13 0.17 0.23 0.34 0.10 N.D. 0.31 0.12 1,335 392 535 11 53 308 2 0.21 0.11 0.09 N.D. 0.17 0.14 0.40 0.14 0.17 N.D. 0.22 0.22 1,864 427 438 8.5 32 561 3 0.40 0.32 0.24 N.D. 0.28 0.30 0.37 0.19 0.15 N.D. 0.38 0.17 3.0 2.0 1.0 0.03 1.0 5.0 2006 1~43-5 TCLP L No. 1 187.5 67.8 64.0 0.4 6.8 23.6 3.1 1.9 1.1 0.4 0.8 0.6 2 197.8 100.4 44.6 0.1 15.4 17.1 4.9 1.5 0.8 0 0.4 1.8 3 278.8 89.8 64.8 0.3 3.8 15.0 5.1 2.0 1.1 0.1 0.5 0.4 TCLP 15.0 5.0 1.0 5.0 伍 結論 TCLP -84- 九十八年六月
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