J. of Korean Inst. of Resources Recycling Vol. 18, No. 5, 2009, 44-51 > ARMBR < BFASHA Te] XY FA42) HS Fst BA Ru wy SRL TROIA, DERE BRE Set stem. peak ANE RAL Nitric acid leaching of electronic scraps and the removal of free nitric acid from the leaching solution for the recovery of copper and tin. ‘*Jae-Woo Abn and Jae-Seong Seo Dept. of Advanced Materials Sci. & Eng., Daejin University 2 & ep sislel 71k SHE Ales. HoMs WS o1eele| Hal ALE AG SESS Alsiat NA SAAS AV) eal. clad ad a 2] TBPS 1B sie} HAMS Hel - FHS] ANSE) Ae 712 a asa. AW ast 3040 M a Tle KALE ASA F WMO, a MSA F RIALS OO THA Soh SHV HEo1 7HssIRT, #71 ol F3 AY) ne FHF oI) Wise Aaalealoe Ago] 7Healga. PMOL: aizaa, Was, SURE, I, Fe, 4 Abstract Fundamental study has been made on the recovery of copper from the electronic serap by hydrometallurgical process. Nitric acid was used as a leaching agent to dissolve the metals such as Cu, Sa, Pb, Fe etc, from the crushed electronic scraps. TBP ‘was employed to extract nitric acid from the strong nitric acid leaching solutions and to reclaim nittic acid, From the exper- mental results, Cu was effectively leached by 3.0-4.0 M nitric acid. And 95% of nitric acd in the Ieaching solution was extracted by 60% TBP, and 98% of nitric acid was stripped from the loaded organic phase by distilled water and it was possible to reuse as a leaching agent. Key words: Electronic scrap, nitric acid leaching, solvent extraction, recovery, Copper, tin, LA 2 Nh. BH OE aIBME SH] ASS ol a, #4, oe, Bo] A7kase] eso} slo} ol salel 2 Alelp), $8) HEalo] HRBo} gE cycle®) slo} wie} sta7] -abAy7171 S34 2 Ho) a4 Be aniles Us +o) Jest: Fe) 71821 WARS) TEST YOU ole HS aPBe A yekEate aR Stee) lez ARE a 2 71e9] IMs elated BBA Az UES] Polch. 8] 21447] Vea BB aMlsie| aa —_______ 818 8 Ic $3} Zo] sbgee] Be WEY "2otord si sil 24, 200md 9 29%) H a4 8 DRS] Be aH] eal ae +P pleco soar aiglola) cies] Sasicks @ + ake. eAae © alt ahieis) weiaiel wala} aabdee|‘Specs Fel SL Alo) le Heh SRE A Raby MAESNE Ra 45 ESE) A7HIS AG 712 OE ASA! Sls Ue ABA eT IT, RACE Gaza & esl ATS Aes ey} lou 82] HPS Als ob] 71Go] ole Het @ + Meh. HY GABAA ola Fe] gt HA) So] Uo FHS HF GH ake BRS Mat BAR AES AIR. SIBG Sle) GASY Oete] Pel, ey 9) F7ESE Seer] $18 3 ei BA So] a Ae] BUS 7A F AT BS SSO) Hh SE Bale Ve Told. Wawa Fe] SS VSA77) WAG FE AA? BH Se o} Se 71d Deve] aie wel} Ayala TAS Bey] gle WY 71k APaavh 23} sleh. 2 Ato ME Va) HGS] BE fo] EE EE Aas] MSV Fels ads ose} AAawol fhe] ASS ash | A YSZIS Beha} sisich, a, aoz HBO Geo] Fe] SS BOY] OME BRE 2M, dewey, Ay, aa Se ae + Deh ey ola BRS Agel ae Geet S| -BAkSe7} 7] HEA BY] Se]zbe Abo} AAAI Meh. o] BF HHS Waele Sap a AAA AVASSL BLOU} Az|ELBo] ww7}o| HERE A) AES Weller she S EE aoe BAS We + sich ae}y GEASS] Ge Bap ASS Hae Be) Sse} MGs Yeo] @ Asie. clo Het AepUeoe Babalehyal spate} BUS APT Uo) GBS SKS BAYS} FEMS 10°C oe] WEEE Zl AA ae & art WS A So] HS Bpshe Yeo] al Uh Eth o1SGSMPANS oleate} ashe why sh Alanine’) 4718S $}Ss}e} 843s yy! Zo} ArH 320), Tene REA BALES ol] ALG Sesh AES A¥slz ae. sey ol BUSS UEcIZe] Gay eas AT 371 eo] ASA) Bat ee ely ally SS we} Bio} Aslalel AeeLe USeHoF aie. he SoS Wo] Ast Sle Be aa mel a Be] Qejos SUE 71Go] Bo] BEST gle wey B ae opie Waleed IVs) Hela] AA La BSG Hol SUFRUES Ase} 712 GES A A]a1iCh. HBAS. TBPCTrien-Butyl-PhosphateyS+ AFB ao] aalesss) qeldee aeaios 2g. at aa + le 3 208 eae Asaion ale ABET + Le Yael Hehe} wash) Aisi. 2. Aeetel 24. AB, AALS FES 3Pel71 HH ABE ASR 4 SMS) ASA) Balelsiol BAG F 4.5mm Bz Sat NS A each Ae] Bet) Ale Table 15} G2") Fe] EMF-so] 22,572 mg/kg 2 7M} Bebst, aoe Ae] eo] G2 yeeteh. 22. Mths St AIASHS FSS] ee BA Bede ave olesle] Fe], 74, of, ae, Ud, Bele 52] HS) WARS BAe] Wh EAA) Het LO L BRA) eS 71S ALE | aedue 2) Aste. dd) A aes & BAEK (pulp density} 100 gL, AASES LO M, 20 M, 30 M, 40 M = See Wsp]zo. OL USREE SOCK Hae] Ae aloha. we PAR FH UA} ABS AAA Fe SASS] H AVB49] FES ICP-AES(Unductively Coupled Plasma Atomic Emission Specttophometer : PerkinElmer, Optima 4300 DYE AMS] WHEE 2} TS] DBSS sealele. 23. TBP Ol 2[8t Bt #2) MASI AS FS - Les) Mel HS ALS TRPS Sf} Sabo} ARS Shah. Eelel-oH) AAS] FEN A7VES SR SCH] 30871 whet E Betadad lo] OF 3082) Bale] Mas Fr WIS Besse. bl Sask Btls) SRS O.IN NaOH BESULS BBs] WAYS, 7) ‘Table 1. Concentration of elements in samples (Unit : mg/kg) Element co Fe ‘Sa Pb Za Al Ni Cone, 22,572 36 1.208 1.64 2,625) 5271 28 agepiolee a 1 @ Fe + 3HINO, Fe(NO3)y + 3/2H) © Sn + 4HNO; H:Sn0, + 4NO; + H,0 © 100 -_ - ~ 80 - OMHNO, . 8 © 20M HNO, a 8 . S 20M HNO, z° 2 -¥~ 4.0M HNO, 5 . 2 £ - 4 2 & 3 —. 3 ° 30 Time(iin.) Fig. 1. Leaching % of Copper at various HNO, concentration with time. (pulp density : 100 g/L, 50°C) J. of Korean Inst. Resources Recycling Vol. 18, No, 5, 2009 Cone. of HNO,(M) Fig. 2 Leaching % of metals with HNO3.(pulp density = 100 g/L, 40min., 50°C)PTA Fe] LEAS) US AL AR SL ON SRI ee a HE, FA DAE (metastannic acid)?] BE TH MESSE Zo] OF LSM SAhe a7pere ee) 4a) ASV) WEY FASB FA] BE7} 7S. HySn0, + 6HCI HySnCl, + 3H,0 o od] AHS TE AS olga AjAayoe Be VESTS DEANE Bt 3.040 M OB 7 ast ¥, lt, Ua zea ae AOe YSl7) DRM FAS DV F GAS Se TS BSS BH FAS AS F ARVN APE Wee] URE Ao ee. Fig. 30: 24t 3.0 M, SO'CO BES wislol, Ge Feo] VSe wa} Fels YeRI agelt}, POEYE HSE 50 ol WU BH 85%9) 7 2 ASKS BO|D WHEE 7 Me} pah9} See) Geshe BBS Bola We. Bey Dye S50 g/L SF 100 gLolA] Fels] BER Aol7} a 2 G7] FEl 100 g/L 2] AP7} Be} REAoe}a Bea. Fig. 4°] P= Att 3.0 M, S95 100 g/Lel Ay Tema] we} Feo] dee wale ded Aolch. AYLSHE] LE} S7 el we} elo} 2 S80] Sb WD EN] SoC Mle DHE) FAA BR: BIS Bolt SHCHMIAE AS & Py} 24 Vte As VF eh. HEY) BS SEE SOCE A4]8h= Ze) Mechs AZ}. Oa, dish} 30M I Ae Ase) Asa Y As} SMO] SES Table 2] VERA. Hele) AY SL 186 9LE VF BRL, ote] 238g, del 158 g/LZ lon Ho] AHE JS4 Sol O.1 glee so} AeA) BS} 7hs sch. SA, o} BF BY) SEM BE PE WRF Bd] SE eat) eelch, 3.2. BABY TBP O! Ost Bat Hel AASAQHY F2] FS AOE All FB SH] BFS Fo] BASIS Geel Tes Hey] MM ASA] Ealske FV] aS AAD BA} Dy. Vaz YSyo| Ah S730 M ole) 4 Be042] pkt Stol(pH 0 9) 8h Fz) & FSop 7} Nach. Woz Fz] FEAE Wel AMEE QUE LIXGE ©] So] FETS FEA 4 B49] pH7E 25-30 FS} wets) atch. ole BH of aos Jee HAC SS ols) SSE +00 109) 2 80 8 3 a) $ 60 2 2 : 40] 2 40 & § 2s) 20 ° Q 0 00 70 Pulp density (9) 200 Fig, 3. Leaching ‘ of Copper at various pulp density (3.0 M 0 80 cy ‘Temporaturet°C) Fig. 4. Leaching % of Copper at various temperature. (3.0 M. HINO, 50°C, 40 min) HINO, pulp density : 100 g/L, 40 min.) ‘Table 2. Composition of leaching solution(3.0 M_HNOs, 50°C) Cu Fe Sa Pb Za Al Ni Initial Cone. (ppm) 22,572 36 1,208 6s 2.625 5271 238 Leaching solution (ppm) | 18580 26 116 1585 2.380 1125 EE] Leaching pereentaget%) 823 722 96 964 907 213 982 aigtepiolZe al 18-2 al SZ, 200948 # AMAA AAS YOY Az") Bo] Bo) Sa = @ BME SAAS Aelshs Hao] 2} BALA} EAE ach. Geb) 7eAlele 232) Keae al Adkel ASSKS Ro] wigs oF Veh. wa PS ss] F4e] Wash. Wile] AWSES Us Ue Blo] Ghose guypaue agepz7p OAT. DAS SHFSSVS o]8she] Mo} aA wt ASS FA] L7HSIO} QLOn}, 4k 3} Fo) AMES. SLE EASE TBP, Alamine336 2X Cyanex923 $0] eh. = ape "24 74] Adetsz Jal Ae + Me TRPS Abele} BGS BA S¥ol Ol Ate alealc. TEP Sse] Ate FEO Zs + did FESS ces} Be] yeha + eh. (TBP)ag + (HNOs)qy = (HNO3: TBP org ®) Rg. Se WiHlsdoe vel Felase] Be] - Fe 7E3S LAV) Alo] TRPEEE $7132) 70%7) A) BPA 7A 2a BZ} BOLL SS) READE = Sasi} Geb aabelch. TSS] Wks e7} 40 Mel 4? 2AQSS4e] TRPSS7} 7K) Ge} a 2] FERS STATS Bolt UF, 70% TBPHAL oF 356A] BO} Ue}. Beh} 0] BF REA Zo] SAH: Fe] F2] BHoLSS $7] ALS AY FSSA] Soh Aibyerio] Re] FS °°] 7Rssithe AS Bele + gated. Fig. 6& Aths= sh) oe} BSH ¥, So} Exe 4, Hl S HHel28o] REAR EB. tea, & PR Ase]. BHLeye AAheE7t OS M ole 7 BF AS AND el, TH, oF a9] Ae HLS A FES) BE BBS B lat Sich. ey Bake E7} 0.05 M oles ae we} wt at 419] FS80] Bey Sz athe 7¥ 001 M WA 20%8 H7ILZ FETE Bah & BolD eh. leet Ashe Relate] Hholew U 2442S Fealel TEP FE57] Ge), a Avge] LBS FH] HD Fol BSS) FSS] WED Azshed, lee ae at S44 28, 8, U8, Pehr FSA) NE Baslo} ae. Wey] o}] Baers] Weel] ake a WLS Isp) Mls AwlSels Akeevh 01M SEs Yor! WP) AAheS Hse Ze] ere MRS apshed) Ageictst dt + Veh. Fig. 72 U442e Whe +e0 BF leadoe FSCSE AV] WBE McCabe-Thicle Diagram’ YepH Aolch. ays} Ge] 27] Bla F a AYSE7) 250 g/L (4.0M)21 3 60% TBP 213i A/O#)7} 13°14 SEEREE, AVOH]7E 1/29) 89-9 FEE 5% VI} Ark] FEO) 7Hesiths AS Tt FU. o] AF TEAS BkSS7t 02M BES) 7\ Geo] JSY) Sashes Fe) sd Fe] Bho} 28S Aol Fes) Valet. ARBESVI Ws TSR Adel THe at SARS] HE HH) SrA S22 Ah BAS aot Uh. TBS] BE wides +S Aft}. Fig. 8& ath] Fee HVHMOETE ne ce ci ‘TBP Concentration Fig, 5. Effect of HINO, on the extraction of metal ions and HINO, (O/A=1, 25°C, 50%TBP) J of Korean Inst. Resources Recycling Vol. 18, No, 5, 2009 ® ® © Pal « . i x . = Fe 3 a °F eee zl ee ; Be re ba i ea a 1 = HNO3) : Lt ; 5 5 - oe Cone, of HNOS Fig. 6, Effect of TBP concentration on the extraction of ‘metal ions. (O/A=I, 25°C, 40M HNO3)FEASaOM Fe] 5) PHS] MCS Sie ee an DRA SME i SHS lssie] WAU AS EA GA BES U3} 48H MeCabe-Thiele Diagram HERE 20) U MHS Wh Teele] Fg] at 9) 1.25 M Heel 3+, 2olAls} Zo] O/Ay|7} 2 OWA FESS HVE BAS 98% O'S BAS WH th. ©] BH GAcls] Akewe 25 MAE EZ SSslo] GVS4o= WHS) Heathe WS t+ at. ae, WHSIl Whe ates Fe] Bae HNO, in Oraanicto/t) Kania, oe HNO, in aquecusta/l) Fig. 7. McCabe-Thiele Diagram of HNOs extracted by TBP. 25°C, 60% TBP) PCB Shreds Recycled HNO HNO, Leaching 9 BelRse] Sasi] Steel lee ASA Fe) S Assy] MANS TIS Woe FSI +H ah = LIX 848 188 See Yeo] Re jole}s YB zhath, LIX 848 AHS Soleel 712 aS BR Ala) alate o}P] We] dela soi, clo a @ Myashs FH VED aaolch. Fig. ote att MSVS 18se] Fel} F44S Behe Meee) PRES VENI. BIS olSe) ASE F BSA 200: a 8 8 HNO, in Aqueous (/l) B g 2 ico a 8 HNO, in Organic (o/D Fig, 8 McCabe-Thiele Diagram of HNOs stripped by water. 250) (3.0 MHNOs, 100 a/) Residues SL Hel Leaching _|——+[Sn Recovery Leach Lavoe Extraction Ratfinate_ | Solvent Exraction of cu fie, 6 stages Loaded Organic | (HNO) Elecrowinning Stipping of Copper ~ [Lovee 4 stages Water HNO, Fig. 9 Hydrometallurgical process for the Cu Metal (99.9%) recovery of copper & tin from eiectronic seraps. Aslepio}aal AL 18-3 al 5%, 200050 Bek te, 2} FAAS TRPE O81 Helsto] At BS = MBAS, A] AAG ASHI BPS Ys} SAAAWS Aa te) BOR BP} 7s sp uo. tH, ale Wie edste +4 ade (metastannic acid)®] BFS BAS ols) ABZ) # ajay ely He Asay Se olga) Fy PALS Hy} hese. 4a AAAs Saye] ANTS Sl TBPS St Fat ay aWeeyel ches} Be AES Asie}. 1) 4, BO, Fe] FS sabe] slal viz 4] SEO] SNOU, FH, DFO SS BS) Aste. 2) Fel] BS WSS SH we} ABEO) S72, AAt LOMA 20%0]819] TES EHH 20MM 30%, 3.0M ots 85% ©] 49] SE TSS Heh. 3) BASE ST + FH Fel] SRS B49} BR, £= S7ke Fel] JSR S7VIAG. o] B FAY DHSS 100 gL MT, BE STO A SHAT. 4) AISA 60% TRE Bs FED BH AlO¥I7} 1/391 734 Set 8H 95% o]t2| Behe PEE Ao] HSA, oleh DSc] Salshe 4, Fe, Yh, FA BS AAeS EZ} 01M ogee TBP ol 1a FSsI7] Valet. ER Topol le) HOE SZ 9) BS SFA ES a) Qt B71 MEO SE a BAAoS NPsle] MBG) 7hssithe AS Be) ssc. AR OAR o] SRS 2000 HMR SEALE 21Ro} 218 AaIUeh. ele BARE ae 1. Sum, B. ¥.L., 1991: The recover of metal from electronic scrap, JOM, 43(4), pp53-61 2. Hoffman, J. E, 1992: The recovery of metal fiom electronic scrap, JOM, 447), pp43-48. 3. Andrea Mecucei and Keith Scott, 2002: Leaching and electrochemical recovery of copper, ; lead and tin from J. of Korean Inst. Resources Recycling Vol. 18, No, 5, 2009 10. . 2. 4 15. 16, scrap printed circuit boards, J. of Chemical Technology and Biotechnology. 77, ppi49-457, Maurice C. Fuerstenau, Guoxin Wang, 1997: Selective scparation of tin from a chloride leach solution, Hydro- metallurgy, 46, pp229.234. S. M, Saleh, S.A. Asid and M.S. ElShahawi, 2001 Extraction and recovery of Au, Sb and Sn from lectrorefined solid waste, Analytica Chimica Acta, 436, P6977 ‘A. Mecueci and K, Scott, 2001: Electrochemical recovery of copper, lead and tn from a nitrate and chloride leaching solution of scrap printed circuit boards, Electrochemical Society Proceedings. 23, pp293. M. A. Rabah, 1998: Combined hydro-pyrometallurgical ‘method forthe recovery of high leadtn/bronze alloy from industrial scrap, Hydrometllurgy, 47, pp281-295. Jae-Woo Ahn, Meong-Woon Kim, Jin-Ki Jeong, Jae-Chun Lee, 2006: Recovery Cu and Sn from the bioleaching solution of electronic scrap 1 of Korean Inst. of Resources Recycling, 15(6), ppAl-47 Le, Long Hoang, Yoo, Kyong-Keun, Jeong, Jin-Ki, Lee, Jae-Chun, 2008: Leaching of copper and silver from ground mobile phone printed circuit boards using nitic acid, J. of Korean Inst. of Resources Recycling, 17(3), ppts-ss, Min-seuk Kim, Jae-chun Lee, Jin-ki Jeong, Byung-su Kim and Eun-young Kim, 2008: Leaching of Copper from Electronic scrap Using Electro-generated Chlorine in Hydrochloric Acid, J. of Korean Inst. of Resources Recycling, 14(5), ppA8-55, Jae-Woo Ahn, Myeong-Woon Kim, Jin-Ki Jeong, Jae-Chun Lee, Dong-Gin Kim, Jong-Gwan Ahn, 2005: Biological leaching of Cu, Al, Zn, Ni, Co, Sn and Pb from waste lectronie scrap using thiobacillus ferrooxidans, J. of Korean Inst. of Resources Recycling, 14(1), ppl7-25. Jae-Woo Ali, Jin-Ki Jeong, Jae-Chun Lee, Dong Gin Kim, 2005: Bioleaching of valuable metals from electronic scrap using fungi(Aspergillus niger) as @ microorganism, J. of Korean Inst. of Resources Recycling, 14(5), pp24-31 Norvell J. Nelson: Regenerative copper etching process and solution, U.S. Patent, 4545850 CJ Brown, D. Davy and PJ. Simmons, 1980: Recovery of nitic acid from solutions used for treating metal surface, Pating and surface finishing, 2, pp60-62. ‘TK. Mattila, 1977: Nitrate removal from waste solutions by solvent extraction, Ind. Eng. Chem, Process Des. Dev, 16(4), pp469-472. M. Hoshino, 1986: Nitric-hydrofluoric acid recovery process of solvent extraction method, Aromatics, 38(10), pp27-222.RRQ Fe] 49) TS ake Sk SL Bato SUMNER ek EE, st 17, Jae-Woo Ahn and Sun-Seob So, 2008: Cementation of tin 18, Stefanowies by aluminium from hydrochloric acid solution, J. of 1991: Tin re Koran Inst, of Resources Recycling, 17(2), pp70-75. Napieralska-Zagozds, S. and Osinska, M., ry from an electroplating sludge, Resources, and Recycling, 6, pp61-69. Conserv Rea eee +84 aaa leaget ae sclalatse alealatelah 84} 2 Sel) ue oe az = + Rb dealiehe Aas ae AES @ 2D) #4) Be ARS Museu Beas ee) MOE * EARTH °93 Proceeding(1993) 457%, {20,0008 (The 2th International Symposium on East Asian Recycling Technology) + Ale }STS] 21411994) 4008, (ft: 15.0008 * ei) Ga Lv {RS 40,0008, 50.000811312) Sal AS NOS, WFR AUS AS, 1: BA ASAI, 1V: FA AHAB, VS8 41K A908, Vi: Bal ASS AMOS, Vs SY ASAT, Ws SA A17SS~a96z) + ah Ue S aS ESA (1996) 483%, fH : 30,0008) 2 DALES EVERSI A RAI996) ITH, GE 5150008 x aeolg S-q11907a 14) 3115, AF: 18,0008 © 97 Ul AAS 71ST SA}(1997A) LOTS, ARS: 15,0008 * ARS] EPHOSY M1998 12))395, Rs : 22,0008, 9a] sent * EARTH 2001 Proceeding (2001) 7883), {FR = 100,0008 (The 6th Intemational Symposium on East Asian Resources Recycling Technology) * Qae) AEA} eo] Se ]g 003 2) 312%, HUH : 20,0008, va + POLES UY ASA, 19991) 440%, 6 + 15,0008, » apolzmA LSA], 2004) 578%, ‘Rts: 270008, wala + ato Sa VASA, 2009) 592%, {fitz = 30,0031, aaledoleg Al 18-8 ALS %, 2009