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SPENT NiMH BATTERIES – RARE EARTHS RECOVERY AND LEACH LIQUOR

SPENT NiMH BATTERIES – RARE EARTHS RECOVERY AND LEACH LIQUOR

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Paper on treatment of spent NiMH batteries
Paper on treatment of spent NiMH batteries

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Published by: suturb on Aug 04, 2013
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Acta Metallurgica Slovaca, 12, 2006, (13 - 19)
13
 
SPENT NiMH BATTERIES – RARE EARTHS RECOVERY AND LEACH LIQUORPURIFICATION THROUGH SELECTIVE PRECIPITATION
 Bertuol D.A.
1,3
 , Bernardes
 
 A.M.
1
 , Holeczek H.
2
 , FetzerH.J.
2
 
1
 LACOR-UFRGS, Av. Bento Gonçalves, 9500, CEP 91501-970. Porto Alegre - RS –Brazil,e-mail: Dbertuol@gmail.com
2
IPA-Fraunhofer Institute for Manufacturing Engineering and Automation, Nobelstrasse 12, D-70569, Stuttgart - Germany
3
ICET-Centro Universitário Feevale, RS 239, 2755, CEP 93352-000. Novo Hamburgo - RS –  Brazil, e-mail: Dbertuol@gmail.com
SPOTREBOVANÉ NiMH BATÉRIE – ZNOVUZÍSKAVANIE KOVOV VZÁCNYCHZEMÍN A
Č
ISTENIE LÚHOVACIEHO ROZTOKU CESTOU SELEKTÍVNEHOZRÁŽANIA
 Bertuol D.A.
1,3
 , Bernardes
 
 A.M.
1
 , Holeczek H.
2
 , FetzerH.J.
2
 
1
 LACOR-UFRGS, Av. Bento Gonçalves, 9500, CEP 91501-970. Porto Alegre - RS –Brazil,e-mail:Dbertuol@gmail.com
2
IPA-Fraunhofer Institute for Manufacturing Engineering and Automation, Nobelstrasse 12, D-70569, Stuttgart - Germany
3
ICET-Centro Universitário Feevale, RS 239, 2755, CEP 93352-000. Novo Hamburgo - RS –  Brazil, e-mail: Dbertuol@gmail.com
Abstrakt
V tejto práci sa študovala možnos
ť
hydrometalurgickej cesty získavania vzácnychzemín a tiež jednoduché metódy získavania bohatých Ni-Co roztokov z použitých NiMH batérií.Aktívny materiál oboch elektród sa odobral ru
č
ne z akumulátora a lúhoval na trepa
č
ke po
č
as 4hodín pri 90°C v 2 M roztoku H
2
SO
4
. Použil sa pomer kvapalnej ku tuhej fáze rovný 1:20.Výsledný roztok z lúhovania mal nasledujúce zloženie (g/L): Ce 3,0; La 2,1; Nd 0,76; Pr 0,63;Ni 22,3; Co 2,4; Zn 0,76; Fe 0,0465; Mn 1,22. Po zrážaní pri pH 1,2 sa získalo viac ako 98 hm%vzacných zemín obsiahnutých vo výluhu vo forme sulfidických solí. Tieto výsledky súporovnatelné s výsledkami publikovanými v iných prácach, v ktorých bola tiež použitákvapalinová extrakcia. Navrhovaný proces okrem toho, že je
ľ
ahšie realizovate
ľ
a viacekonomický, nie je navyše v porovnaní s kvapalinovou extrakciou hrozbou pre životnéprostredie.
Abstract
In this work a hydrometallurgical route for rare earths recovery and a simple methodto obtain a rich Ni-Co solution from spent NiMH batteries were evaluated. The active materialsfrom both electrodes were manually removed from the accumulators and leached in a 2 MH
2
SO
4
solution at 90°C under agitation for 4 hours. A 1/20 solid/liquid ratio was used. Theresulting leaching solution presents the following composition (g/L): Ce 3.0; La 2.1; Nd 0.76; Pr0.63; Ni 22.3; Co 2.4; Zn 0.76; Fe 0.0465; Mn 1.22. After precipitation at pH 1.2 more than 98wt% of the rare earths contained in the leached solution were recovered as sulfate salts.Considering the whole process, with precipitation at pH 1.2 followed by precipitation at pH 7,around 100 wt% of iron and 70 wt% of zinc were removed from the leaching solution. These
 
Acta Metallurgica Slovaca, 12, 2006, (13 - 19)
14
 
results are compatible to those found in the literature when solvent extraction was employed.The proposed process, besides being easier to handle and more economic, does not present theenvironmental threats that the solvent extraction presents.
Keywords:
Recycling, NiMH batteries, Rare earths, Metal recovery.
1.
 
Introduction
The progress of electronic technology in the last decades has been remarkable, andhigh hopes are held for future achievements. As a part of this, there is a great increase inelectronic scrap generation, such as obsolete computers, cell phones, mobile devices andconsequently batteries.All types of materials present in a battery will contribute in some way to increase theenvironment pollution when discarded. Some of them, such as carbon, are not so aggressive tothe environment and can quickly merge into the ecosystem without noticeable impact. Othercomponents, such as steel, plastics and fabric, while not actively toxic to the ecosystem, will addto the volume of a landfill, since they decompose slowly. Of most concern, however, are theheavy-metal battery components, which, when discarded, can be toxic to plants, animals, andhumans. Cadmium, lead, and mercury are the heavy-metal components most likely to be thetarget of environmental concerns[1].The NiMH batteries are considered environmental acceptable, since they do notcontain in their composition highly toxic metals. This fact combined with the better performancepresented by NiMH batteries makes that NiCd batteries were substituted by NiMH in largenumber of applications [2]. The NiMH operation system is based on the NiCd batteries system,where the Cd electrode is substituted by the MH (metal hydride). The typical examples of MHalloys are AB
2
, that is basically an alloy of TiNi
2
, and AB
5
, that is basically a LaNi
5
alloy
 
[3].For economic reasons, La is substituted many times by a rare earths alloy [4].Due to the great increase in generation of spent NiMH batteries the recycling of themetals content present in their composition should be studied, avoiding the disposal of tons of dangerous waste [5]. The goal of waste minimization combined with the economical value of metals such as nickel, cobalt and rare earths, requires the development of efficient recyclingprocesses. Therefore, the recycling of this kind of waste, besides bringing profit inenvironmental terms, can also bring benefits in economical terms.The purpose of the first step of this work was to study the rare earths recovery byselective precipitation, determining the optimal pH range for the precipitation. The second andlast step consisted in the purification of the solution obtained after the rare earths recovery,aiming to obtain a rich Ni-Co solution, with low concentration of contaminants as Zn, Fe andMn. A literature survey reveals that there are some solvent extraction processes that areproposed for the recovery of rare earths as well as to remove contaminants [6-7]. These includethe use of the many different process parameters as well as different organic compounds.
 
The method proposed in this work is a simple alternative to the use of solventextraction. The recovery of Ni and Co from the purified solution can be done by anelectrochemical process where Ni-Co alloys with different compositions can be obtained [8-11].
2.
 
Experimental
2.1 Leaching
Cylindrical NiMH accumulators type AB
5
, were used in this work. The accumulatorswhich weighed an average of 18.5 g where cut in half longitudinally. After removal of the
 
Acta Metallurgica Slovaca, 12, 2006, (13 - 19)
15
 
external stainless steel case and the perforated plate from the negative electrodes plus the fabricseparator [12], the positive and negative electrodes were manually homogenized and leached ina 2 M H
2
SO
4
solution at 90°C under agitation for 4 hours. A 1/20 solid/liquid ratio was used.After leaching the insoluble residue was filtrated and washed with water. Sulfuric acid wasemployed as a leaching agent mainly to prevent iron dissolution, an important competing ionduring the selective recovery of valuable metals [13-14]. Total concentrations of the chemicalconstituents of electrodes were determined after their complete dissolution in aqua regia.Leaching data were compared against this standard.
2.2 Precipitation tests
Preliminary precipitation tests were done to define the optimum pH for the rare earthsrecovery. The pH values evaluated were 0.8, 1.0, 1.2, 1.4 and 1.6. These pH values wereselected to avoid the ferric hydroxide precipitation that usually starts at pH 2.5~3 [15].Thequalitative and semi-quantitative chemical analyses of the precipitates were accomplished by X-ray fluorescence (XRF) and its crystalline phases were identified by X-ray diffraction registeredin the interval of 5°<2
θ
<80°. With the solution obtained after the rare earths recovery furtherprecipitation tests were done to evaluate the suitability to remove Zn, Fe and Mn leaving Ni andCo in the solution. The pH values evaluated were 5.0, 6.0 and 7.0. The precipitates in all testswere obtained by NaOH addition. The rare earths concentrations were determined by inductivelycoupled plasma-atomic emission spectroscopy (ICP-AES). The concentration of Ni, Co, Fe, Mnand Zn were determined by Ionic chromatography (IC). These elements were selected because aprevious work has shown that these elements are the most abundant in a NiMH battery [12].
3.
 
Results and discussion
3.1 Leaching
Table shows the results obtained in the electrodes leaching. As expected theuse of sulfuric acid resulted on a poor extraction of iron. Another important factor thatcontributed to this low iron concentration was that the external case as well as the perforatedplates from the negative electrode were removed before leaching. The metallic alloy that theseparts are made contains a high iron concentration. Previous results indicated that in realsituations the external cases as well as the perforated plate could be removed by magneticseparation [12].
Table 1 Leaching yields obtained using a 2M sulfuric acid solution, at 90°C for 4 hours.
Element
CeLaNdPrNiCoZnFeMn86.3682.591.2291.0492.3195.7253.330.63
Aqua regia [g/L]Sulfuric acid [g/L]
0.08721.3422.32.40.76220.0465
Extraction %
79.753.6383.332.50.882.10.7684.00272.60.79630.79
 
In this work, despite the use of experimental conditions very similar to the ones foundin the literature, a smaller amount of the material was leached [6]. For Ni, a higher dissolution

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