ELECTROOBTENCION DE METALES

1. INTRODUCCION
Los metales se obtienen de sus minerales naturales por
reduccin, la cual podra ser siempre electroqumica.
En la prctica se pueden preferir otras vas (reactivos
qumicos, carbn o metales activos)
Eleccin sobre una base econmica, considerando la
pureza requerida del producto, su forma fsica y el resto de
las etapas del proceso global de obtencin (tratamiento y
concentracin del mineral, separacin luego de la
reduccin, refinacin y fabricacin).
Consideramos los elementos que pueden ser preparados
comercialmente segn primer paso de su separacin por via
electroqumica.
El solvente no reacciona en el ctodo H2O slo para
elementos poco activos
 1.1 Electrowinnig en solucin acuosa
(a) el mineral es convertido en una forma soluble en
cido, usualmente un xido, por tostacin y a
continuacin lixiviado:
MOx + 2x H(aq) M2x+(aq) + x H2O

(b) La solucin es purificada y tal vez concentrada

(c) Las reacciones andicas y catdicas durante la

electrlisis son:
M2x+(aq) + 2Xe M
x H2O x O2 + 2x H(aq) + 2Xe

(d) El cido liberado en el nodo se recircula para el

proceso de lixiviacin.
MOx M + x O2 (reaccin neta)
y no debera haber consumo de cido o agua.

El uso de cido sulfrico favorece la evolucin andica

de oxgeno mientras que el uso de cido clorhdrico
probablemente generara cloro.
La evolucin de hidrgeno disminuye la eficiencia en
el ctodo y consume el cido.
La alta conductividad de los protones solvatados
reduce las prdidas de energa por cada hmica.
No hay otro solvente que combine todas estas
ventajas a temperatura ambiente.
a) La lixiviacin del mineral conteniendo xidos del
metal extrae directamente el metal sin necesitar de
tratamientos trmicos previos (particularmente
atractivo para bajas concentraciones).
En muchos casos la concentracin del mineral por
flotacin seguida del proceso de fundido es tambin
ineficiente y la lixiviacin es ms satisfactoria.

(b) Antes de la electrlisis, remover impurezas de

metales ms nobles (deposicin preferencial) Zn
requiere purificacin ms extensa. Los ms activos
(Mg) pueden tener que ser removidas para evitar su
acumulacin y precipitacin en lugares
inconvenientes. Ojo! Impurezas que reducen la
sobretensin de evolucin de hidrgeno, reduciendo
as la eficiencia de corriente.
(c) En general se realiza electrlisis de soluciones de
cido sulfrico el equipamiento utilizado fuese
bastante uniforme. Pb (resistente a la corrosin) en
recubrimiento de tanques y para los nodos.
Ventaja del electrowinning: produce metal de alta
pureza (sin posterior refinacin).
Bajo catodizacin el electrodepsito no es atacado por
el solvente en sistemas acuosos.
2. PROCESOS HIDROMETALURGICOS
HIDROMETALURGIA DEL COBRE

Depending upon the ore-type used as a charge

Copper can be produced either
pyrometallurgically (copper sulphide and iron
sulphide minerals )
or hydrometallurgically (copper oxide minerals ).

The hydrometallurgical route is used only for a

very limited amount of the worlds copper
production and is normally only considered in
connection with in-situ leaching of copper ores
Para obtener la misma pureza del metal con el cobre piroltico y
el de cementacin que con el resultante de la extraccin
electroltica debe llevarse a cabo una refinacin electroltica.
Todo el cobre comercializado se puede calificar de cobre
electroltico, ya que es bien obtenido directamente por
electrlisis del mineral o bien por refinacin electroltica que
sigue a otros procesos.

Ya que los yacimientos ms ricos se van acabando

rpidamente, se puede predecir que en el mediano plazo los
mtodos hidrometalrgicos habrn reemplazado a aquellos por
va seca, gracias a su capacidad de tratar directamente
tambin los minerales ms pobres.
2.1 Extraccin electroltica de cobre
2.1.1 Aspectos generales
Lixiviacin con cido H2SO4 de minerales fcilmente
solubles y relativamente pobres de Cu (1-2%),
seguida de electrlisis de la solucin lixiviante, con
nodos insolubles de Pb. La evolucin andica de
oxgeno regenera el cido, que se recicla la etapa de
lixiviacin.
Los minerales oxidados para la lixiviacin contienen
algo de sulfuros, (calcosina Cu2S), que no pueden ser
directamente disueltos en H2SO4. Adems la cuprita
Cu2O, reacciona con el cido generando CuO:
Cu2O + H2SO4 CuSO4 + Cu + H2O
Sin embargo, hasta los compuestos sulfurados y el
cobre metlico son solubles en presencia del oxidante
sulfato frrico: Fe2(SO4)3 + Cu 2FeSO4 + CuSO4
La presencia de sales de hierro baja el rendimiento
faradaico. Su concentracin, se fija x compromiso
econmico entre las eficiencias de extraccin y de
electrlisis.

In the hydrometallurgical process, the oxidized ores

and waste materials are leached with sulphuric acid
from the smelting process. Once the copper-rich
solutions are collected they can be processed by
the solvent extraction / electrowinning process
(SXEW).
SX/EW process (dissolution, solvent extration, electrowinning)

A concentrated, pure copper sulfate solution suitable for

electrowinning is produced from the initial leach solution by
selectively transferring the copper ions to an organic phase by a
process known as solvent extraction and returning them again
to an aqueous phase. Complexing agents are dissolved in an
organic solvent and this phase is intimately dispersed within the
aqueous leach solution in a mixer/settler. The copper selectively
complexes with the reagent [but not iron and other impurities]
and is transferred into the organic phase. The copper replaces
hydrogen on the complex and H+s are consequently transferred
to the aqueous phase. The two phases are allowed to separate
in a settling tank and then the aqueous acid solution (raffinate)
is recycled to ore leaching. The loaded organic phase is sent to
a second mixer/settler where it is reacted with a strong aqueous
sulfuric acid solution. Here, the copper is exchanged for H+ and
transferred into the second aqueous phase. The copper-rich
strip solution is passed into an electrowinning cell.
A remarkably good materials balance can be
obtained from such a flowsheet for the
production of copper when a highly selective
organic acidic complexing agent is used.
 Materials balance in a sulfate leach/SX/EW using a
pH-swing extractant
CuO + H2SO4 = CuSO4 + H2O Leach
CuSO4 + 2 LH = CuL2 + H2SO4 Extract
CuL2 + H2SO4 = CuSO4 + 2LH Strip
CuSO4 + H2O = Cu + H2SO4 + O2 Electrowinning

The materials balance (overall CuO = Cu + O2)

acid consumed in the leaching is regenerated in the
extraction step (leachant is recycled)
the complexing agent LH is regenerated in the stripping
step (extractant is recycled)
the acid consumed in the stripping step is regenerated in
electrowinning (electrolyte is recycled)
2.1.2. Electrlisis In a typical operation, the
electrolytic cells are rectangular
tanks and each contains 20-50
negative electrodes and a similar
number of positives. An additional
positive electrode is required in
each cell in order to ensure plating
occurs on both sides of each
negative. The electrodes are
designed to rest on busbars that
supply electricity; these are situated
outside the top of each tank, one for
the negatives and another for the
positives. Thus, the electrode pairs
in each tank operate in parallel. In
the tankhouse, there is a multiple
system of practical sections with the
banks of cells connected in series
and parallel to obtain optimum use
of the electrical power derived from
the rectifiers.
The positive, oxygen evolving, electrodes are usually
made from lead calcium alloys (pasivadas con un
xido conductor electrnico) similar to those in lead-
acid batteries.
The traditional negative electrodes for copper
electrowinning were thin copper starter sheets made by
plating copper onto titanium or stainless steel electrodes.
The copper was then stripped from the substrate and
inserted into the electrolysis cell and copper deposited
from a solution usually containing a concentration of 25 to
60 grams / liter (g/l) copper as copper sulfate and 50 to
180 g/l sulfuric acid, held at 50 to 60oC (122-140oF). Small
quantities of a hydrocolloid such as Guar gum are included
in the electrolyte, as this helps to form a dense
electrodeposit. Typically, a current density of 300 A/m2 is
passed between each pair of positive and negative
electrodes; this gives a cell voltage of ~2.0 V and the
energy consumption is ~2.0 kWh/kg.
Modern developments in copper electrowinning
include the use of re-usable stainless steel
electrodes to replace copper starter sheets. This
technology was established in the Isa Process and
later in the Kydd Creek Process. In addition to
lowering manpower requirements, it allows the
current density to be increased by ~10%. Following
electrolysis, the copper is stripped from the
stainless steel in special automated machines.
In a typical commercial copper electrowinning plant,
there will be thousands of pairs of electrodes in
operation together. In modern systems, insertion of
negative electrode blanks, removal of loaded
electrodes, and transfer to the stripping machines
are fully automated.
Er,O2 / H2O 1,2 V
E 2
r,Cu / Cu 0,3 V.

Por lo tanto la deposicin catdica de cobre,

acompaada de evolucin andica de oxgeno, tiene
en condiciones de reversibilidad una tensin de celda
no lejana a 0,9 V.
Para corrientes de operacin en el alcance 280-340
A/m2, x la resistividad relativamente alta del electrolito
y la gran sobretensin de oxgeno sobre plomo la
tensin efectiva resultante esta comprendida entre 1,9
y 2,2 V.
Porqu Fe baja el rendimiento de corriente?

Los potenciales standard de las cuplas Fe/Fe2+ y

Fe/Fe3+ son -0,44 y -0,036 V, aqul de la cupla
Fe2+/Fe3+ es +0,67 V, y por tanto intermedio entre los
potenciales de nodo y ctodo de la celda de
electrlisis.
la deposicin de FeO no puede ocurrir
la reaccin Fe3+ + e Fe2+ ocurre competitivamente
con la de deposicin de cobre,
la reaccin Fe2+ Fe3+ + e ocurre competitivamente
con la evolucin de oxgeno

cupla Fe2+/Fe3+ exhibe un efecto cclico que perdura

indefinidamente
Traditional pyrometallurgical process:
roasting, smelting in reverbatory
furnaces, producing matte, and
converting for production of blister
copper, which is further refined.
During smelting the concentrates are
dried and fed into a blast furnace.
There the sulphide minerals are
partially oxidized and melted to yield
a layer of matte, and slag. The matte
is further processed by converting,
where the molten material is oxidized
in the presence of air to remove the
iron and sulfur impurities (as
converter slag) and to form blister
copper.
A third product of the smelting
process is SO2, which is collected,
purified and made into sulphuric acid
for use in hydrometallurgical leaching
operations.
Blister copper, containing a minimum of 98.5% copper, is refined
to high purity copper in two steps. The first step is fire refining, in
which the molten blister copper is poured into a cylindrical
furnace, similar in appearance to a converter, where first air and
then natural gas or propane are blown through the melt to
remove the last of the sulphur and any residual oxygen from the
copper. The molten copper is then poured into a casting wheel to
form anodes pure enough for electrorefining.
2.2 Electrorefinado de cobre

Electrorefining is an electrolytic process that involves

anodically dissolving a metal at the positive electrode
in a cell and simultaneously re-depositing the same
metal at the negative electrode.

Se disolver cobre y todos los metales por arriba de

ste en la serie electromotriz (Zn, Fe, Ni, Sb y Pb)
cuando stos estn presentes en el nodo. Los
elementos debajo de cobre en la serie
permanecern no ionizados y por lo tanto, sin
disolver en el nodo, dejando un residuo o barro
andico. Mediante un balance adecuado de la
corriente de ionizacin con el potencial de
descomposicin debera ser posible depositar en el
ctodo solamente cobre.
Los nodos resultan de la colada de cobre blister
(previamente fundido y refinado a fuego para eliminar
oxgeno y azufre, de modo que permita en la placa
andica obtener superficies los ms regulares
posibles).

Como sustratos iniciales para los ctodos se pueden

utilizar placas de cobre electroltico laminado. El
cobre depositado en forma de lminas sobre este
sustrato se retira cada 24 horas una vez que alcanz
espesores de 0,6-0,8 mm.

A problem with the extremely pure copper cathodes

is that they have to be regularly replaced. These are
very expensive and labour-intensive to make. They
can easily warp or bend, which causes difficulties in
production.
Solution: replace starting sheets of copper cathodes
with a reusable stainless steel cathode. Deposited
copper is separated from the stainless steel starting
sheet by use of a guillotine and/or by flexing with an air
blast. The stainless steel cathodes can be reused once
the pure copper has been stripped from them. Very
significant labor-cost reductions have also been
achieved because of the introduction of automated
handling of anodes and cathodes in the tank house.
The ISA Technology allowed for the reduction in
manning requirements, provided superior mechanical
handling systems, reduced copper inventory levels,
permitted a more intense operating regime, improved
cathode quality and offered a much safer electrolytic
operation. It enabled the commissioning of smaller
scale electrowinning operations by making them
independent of starter sheet supplies.
 A view of the tank house
with cathodes and
anodes in place

The cathodes being

returned to the tanks by
the automatic crane.
 A single stainless steel
cathode before it is
placed in the tank

The final product of

the ISA Process,
sheets of 99.99% pure
copper
A current density of ~300 A/m2 is passed between
the negative and positive electrodes and this
results in a cell voltage of about 0.28 V. The
electrical energy consumption in the copper
electrorefining cell is ~0.25 kWh/kg.

La tensin media de celda a 300 A/m2 y 60oC es

cercana a 0,28 V (explicar el alumno porque es
tanto mas baja que la de la celda de
electrowinning de cobre al completar el punto
final comparativo entre las dos industrias)
La adicin de inhibidores al bao en forma de agentes
tensioactivos (gelatina, dextrina, cola, tiourea, aceite de
ricino sulfurado, etc.) es necesaria para obtener un
crecimiento regular del depsito catdico, inhibiendo la
formacin de dendritas.
The adsorption of glue on the cathode occurs mainly at locations
with high field strength (edges, nodules, and needles on the
cathode surface). Electroadsorption of the polar glue molecules
mainly takes place in these areas, forming an isolating layer, and
the field strength decreases. The growth of the needle, which
could lead to a short circuit, is stopped. After the normal copper
layer has grown up to the peak of the needle, the glue is desorbed
and can be adsorbed again in another area with high field strength.
2.2.1 Disolucin de impurezas y formacin
de barros andicos

El cobre andico esta parcialmente combinado con

oxgeno en forma de xidos cuproso y cprico, que
adems se producen por reaccin qumica de la
superficie con el oxgeno disuelto en el bao. Por lo
tanto, paralelamente a la disolucin electroqumica
CuCu2 + 2e , ocurre tambin una disolucin
qumica de los xidos en el medio cido:

Cu2O + 2H2Cu + H2O (a)

CuO + 2H2Cu2 + H2O (b)
Por su parte los iones cuprosos dismutan en la
solucin dando un precipitado de cobre elemental:
Cu + CuCu2 + Cu
Una parte relevante de los barros andicos contiene
cobre metlico.

Las reacciones (a) y (b) aumentan la concentracin

de ion cprico y disminuyen la acidez del bao. Esto
se compensa mediante la insercin, por cada 100
celdas con nodos de cobre, una o dos celdas con
nodos insolubles de plomo.

Ag, Au, Pd, Pt, Se, y Te, por tener potenciales en la

serie ms nobles que el cobre, resisten
apreciablemente la oxidacin andica y se depositan
en lo barros andicos.
2.3 Comparacin entre electrorefinado y
electrowinning de cobre
(Sern completados los siguientes puntos por
el alumno, basados en el terico anterior y en
su investigacin bibliogrfica sobre el tema)
Reaccin qumica
Fuente de cobre
Naturaleza del nodo
Naturaleza del ctodo
Naturaleza del electrolito
Corriente
Voltaje
Consumo de potencia
 The End

Questions?