2.

4Recycling Technologies
2.4.1Metal Recycling Technologies
Electronic scrap consists of highly multi-component wastes containing besides steel,
plastics mostly all main non-ferrous metals such as aluminium, copper, zinc, tin and
lead, ferrous metals and precious metals like gold, palladium and silver. Next to the
extraction of harmful components as lead, cadmium, hexavalent chromium and
mercury are the high trade prices for gold, copper and silver the determining factor for
recovery of the precious metals of electrical and electronic systems. Nonetheless
metal recycling technologies are demanding high requirements to achieve an efficient
output, a proper disposal of problematic substances and a reliable evaluation of the
precious metal contents has to be provided, too.
As exemplified in table 24 precious metals are used in components such as pin

connectors, contact points, silver coated wire, terminals, capacitators, plugs and relays
(PCB components).
Table 24: Metal compounds in EES components
Metal
Main use in EES components
compoun
d

Copper

Conductors (wire harness, coils, electric motors, PCB)

Iron

Housings and structural parts, magnetic cores (in coils, solenoids, motors,
transformers)

Aluminiu Housings of components, heat sinks

m

Lead

Battery (lead acid), piezoelectrical components (sensors + actuators),

solder (PCB, junction boxes and all components soldered to wires),
pyrotechnical initiators, carbon brushes of electric motors

Tin

Solder (PCB, junction boxes and all components soldered to wires)

Nickel

Battery (NiMH), PCB

Zinc

Battery, metal coatings

Magnesiu Aluminium alloys, castings

m
Mercury Discharge lamps (also used in LCD screens)
Silver

PCB components, batteries, heating wires of window heating

Gold

PCB components and electrical contacts, relays, connectors

Palladiu
m

PCB components

Platin

PCB components, electrodes of sensors / actuators

Metallic Wire harness

alloys
(CuZn,
CuSn)
Lithium

Battery (Li-ions)

Tungsten Decandescent lamps

Indium

LCD panels

Zr (ZrO2) Ceramics (e.g. lambda control sensor, piezoelectrics)

Titanium Ceramics (e.g. lambda control sensor, piezoelectrics)
(TiO2)
Other
PCB
(bismuth,
antimony,
tantalum)

In the following chapter the pyrometallurgical processes, which are applied for the
recovery of the major amounts of metals from end-of-life vehicles copper,
aluminium, iron and steel and the hydrometallurgical processes, which are applied
for the recovery and refinement of secondary non-ferrous metals and precious metals,
are described.
2.4.1.1Pyrometallurgical Processes Smelting
Smelting consists of separation and purification of specific metals by means of
heating and treating the scrap fractions. The non-ferrous metals alloys can be treated
by means of pyrometallurgical processes by taking advantage of their different
smelting point meaning that the material is processed in high-temperature reactions to
separate metals from impurities. The heavy fraction of scrap consisting of lead, copper
and zinc can be extracted by selective smelting processes. In general, the extraction of
metals from electroscrap is a complex process, integrated with several process lines to
refine various primary and secondary metals.
The recovery of metals in a selective smelting process is done on special sweating
furnaces (rotary, reverberatory, or muffle furnaces) where the metal fraction is slowly
heated. The oxidation of the finely divided scrap is minimised by a multi zone
temperature control, which allows the controlled melting of the different metals
present [Rosseau 1991].
The TS-process (Trennschmelz-Verfahren) described by Rosseau (1991) for metal
recovery is based on the selective smelting of a particular metal by partial immersion
of the previously dried scrap in a bath consisting of the same metal. Consequently
only one metal can be recovered in each step, starting with the lowest melting point,
followed subsequently by the rest of the components. The most frequent metals
recovered by this process are lead-rich (90 % Pb), zinc-rich (92 % Zn) and copper-rich
(45 50 % Cu) products by the performance of two subsequent TS-treatments.
A variety of furnaces can be used for melting metal scrap. The choice of furnace
depends upon the quality and composition of the metal scrap, the desired production
rate, and the mode of operation desired. Other factors influencing furnace selection
are capital costs, refractory lifetime, and metal losses.
The processing of several metals by smelting processes as listed in table 25 will be
described in the next paragraphs, on the basis of the different furnace descriptions :

Table 25: Overview of pyrometallurgical processes for the recovery of metals

Pyrometallurgical process

Metals

Smelting

Cu, Al, Zn, Pb, Mg

Reverbatory furnace

Cu, Al, Zn

Electric furnace

steel, Fe

Multichamber furnace

Al, Zn, non-ferrous metals

Blast furnace

steel, Cu

Crucible furnace

Zn, Mg

Gas fired furnace

Pb, Zn, Cu, Cd, Al

Rotary furnace

Cu, Al, Zn

Induction furnace

Al, Zn

Blast oxidation furnace

steel

Electric arc furnace

steel

Reverberatory Furnace
Reverberatory furnaces heat the required metals to melting temperatures with direct
fired wall mounted burners. The primary mode of heat transfer is through radiation
from the refractory brick walls to the metal scrap, but convective heat transfer also
provides additional heating from the burner to the metal. Reverberatory furnaces are
available with capacities ranging up to 150 tons of molten metals. The advantages
provided by reverberatory melters are the high volume processing rate, and low
operating and maintenance costs. The disadvantages include the high metal oxidation
rates, low efficiencies, and large floor space requirements.

Figure 56: Reverberatory Furnace

[http://www.osha.gov/SLTC/etools/leadsmelter/popups/blastfurnacelleadtap_popup.ht
ml]
Electric Reverberatory Furnace
Electric reverberatory furnaces are used primarily as holding furnaces. These furnaces
are refractory lined vessels using resistance heating elements mounted in the furnace
roof above the hearth. These furnaces are used for smaller melting applications where
limitations on emissions, product quality, and yield are of high priority.
Advantages over gas-fired reverberatory furnaces include low emissions, low metal
oxidation, and reduced furnace cleaning. Disadvantages include high fuel costs, low
production rates, higher capital costs, and frequent replacement of heating elements.
Multichamber Furnace
This type of furnace consists of two rooms. The scrap is fed into one of the chambers.
In the other room, the metal is heated using a flame, identical to the reverberatory
furnace. Through a system with natural or forced convection, the warm metal is
transported to the room with the scrap. By circulating the liquid metal through it, the
scrap is melted. This type of furnace is mostly used for melting moderately polluted
types of scrap.
Blast Furnace

A blast furnace is a smelting furnace consisting of a vertical cylinder atop a crucible,

into which lead-bearing charge materials are introduced at the top of the furnace and
combustion air is introduced at the bottom of the cylinder. It operates in temperature
greater than 980C in the combustion zone that metal compounds are chemically
reduced to elemental metals (e.g. lead and elemental lead).

Figure 57: Blast Furnace

[http://www.osha.gov/SLTC/etools/leadsmelter/smelting/blastfurnace.html]
Crucible Furnace
The crucible furnace consists of a crucible of refractory material in which the metal is
melted by direct heating with a flame, or by an induction spiral. In order to tap the
furnace, it is turned over manually or by using a hydraulic device. This type of furnace
is used in the recycling industry to remelt thin-walled, clean types of scrap.
Advantages provided by the electric crucible furnace is the near elimination of
emissions and low metal oxidation losses. Disadvantages include increased fuel costs

and size limitation.

Figure 58: Diagram of a crucible furnace with an inward radiating metal fibre burner
[http://www.acotech.com/appl10.htm]
Gas Fired Crucible Furnaces
Crucible furnaces are small capacity, indirect melters/holders typically used for small
melting applications or exclusively as a holding furnace. The metal scrap is placed our
poured into a ceramic crucible which is contained in a circular furnace which is fired
by a gas burner. The energy is applied indirectly to the metal by heating the crucible.
The advantages of crucible furnaces are their ability to change alloys quickly, low
oxidation losses, and their low maintenance costs. Disadvantages include low
efficiency, (as low as 12 %), high emissions, and size limitations [Metal Advisor
2004].
Energy efficiency can be improved by 50 % by adding a ceramic matrix recuperator to
the exhaust system to recover waste heat for preheating the combustion air.
Rotary Furnace
Rotary furnaces are used almost exclusively for reclaiming low grade scrap. The
Furnace operates by rotating the charge through the furnace which comes in direct
contact with a gas burner or with a refractory wall which was directly heated by the
burner. Typical rotary furnaces have holding capacities of 2 to 5 tons and are usually
charged with salt which acts as a flux to improve metal recovery and reduce oxidation.
The advantage provided by rotary furnaces is their ability to process dross and lowgrade scrap which is difficult to process in other types of furnaces. The disadvantages
are low efficiency, higher maintenance requirements, and considerable salt cake
production which must be disposed of as hazardous waste.

Figure 59: Rotary Furnace

[http://www.alliedmineral.com/products/rotaryfurnaces.htm]
Induction Furnace
There are two general types of induction furnaces: channel and coreless. Channel
furnaces are used almost exclusively as holding furnaces. Channel furnaces operate at
60 Hz where the electromagnetic field heats the metal between two coils and induces
a flowing pattern of the molten metal which serves to maintain uniform temperatures
without mechanical stirring. Coreless furnaces heat the metal via an external primary
coil. Coreless furnaces are slightly less efficient than channel furnaces, but their melt
capacity per unit floor area is much higher. Coreless furnaces are used mainly for
melting of finely shredded scrap where they are most cost competitive with gas-fired
furnaces. Advantages of induction furnaces include high melting efficiency (50
70 %), low emissions, low metal oxidation losses, and high allow uniformity due to
increased mixing. Disadvantages are primarily their high capital and operating costs.

Figure 60: Coreless Induction Furnace

[http://www.alliedmineral.com/products/corelessinductioncopper.htm]

Figure 61: Channel Induction Furnace

[http://www.alliedmineral.com/products/channelfurnacecopper.htm]
Basic Oxygen Furnace (BOF)
The BOF is a pear-shaped furnace, lined with refractory bricks, that refines molten
iron from the blast furnace and scrap into steel. Up to 30 % of the charge into the BOF
can be scrap, with hot metal accounting for the rest. Scrap is dumped into the furnace
vessel, followed by the hot metal from the blast furnace. A lance is lowered from

above, through which blows a high-pressure stream of oxygen to cause chemical

reactions that separate impurities as fumes or slag. Once refined, the liquid steel and
slag are poured into separate containers. The main advantages include its rapid
operation, lower cost and ease of control.

Figure 62: Diagram of the Basic Oxygen Furnace

[http://homepage.tinet.ie/~jcelce/subjects/metalwork/pages/bop.html]
Electric Arc Furnace
An Electric Arc Furnace is a steel melting furnace in which heat is generated by an arc
between graphite electrodes and the metal. The basic material is metal scrap in place
of molten metal, and both carbon and alloy steels are produced. Furnaces with
capacities up to 200 tonnes are now in use. The Electric Arc Furnace (EAF) offers an
alternative method of bulk steel manufacture, utilising scrap as a metal source, e.g. car
scrap.
The EAF has evolved into a highly efficient melting apparatus and modern designs are
focused on maximising the melting capacity of the EAF. Melting is accomplished by
supplying electrical or chemical energy to the furnace interior. The melting point is
reached at around 1520 C and the steelmaking efficiency is about 55-65 % [Jones,
2004].
The first step in the production is to select the grade of steel to be made. Many
operations add some lime and carbon in the scrap and supplement this with injection.
After the scrap is loaded in the furnace, the roof is lowered and then the electrodes are

lowered to strike an arc on the scrap, this commences the melting portion of the
cycle.
Once the final scrap charge is melted, flat bath conditions are reached. The analysis of
the bath chemistry will allow the melter to determine the amount of oxygen to be
blown during refining and arrange the alloy additions to be made. Refining operations
in the electric arc furnace have traditionally involved the removal of phosphorus,
sulphur, aluminium, silicon, manganese and carbon from the steel with the addition of
oxygen throughout the cycle, as a result some of the melting and refining operations
occur simultaneously. In recent times, dissolved gases, especially hydrogen and
nitrogen, has been recognised as a concern. Other operation include the oxidation of
impurities by de-slagging [Jones, 2004].
Once the desired steel composition and temperature are achieved in the furnace, the
tap-hole is opened, the furnace is tilted, and the steel pours into a ladle for transfer to
the next batch operation (usually a ladle furnace or ladle station).

Figure 63: Electric Arc Furnace [http://www.steel.org/learning/howmade/eaf.htm]

The following section characterises the individual smelting procedures by metal type
present in automotive EES:
Copper Smelting
Low-grade copper scrap is melted in either blast or rotary furnace resulting in slag and
impure copper. The smelting point of Cu is approximately 1080C. In the blast
furnace, the copper is charged to a converter, where the purity is increased to about 80
to 90 %, and then to a reverberatory furnace, where purity levels of 99 % are achieved
[EPA 1995]. In these fire-refining furnaces, flux is added to the copper and air is
blown upward through the mixture to oxidise impurities. Then by reduced
atmosphere, cuprous oxide (CuO) is converted into copper. Fire-refined copper is cast
into anodes, which are used during electrolysis. The anodes are submerged in a
sulphuric acid solution containing copper sulphate. As copper is dissolved from the
anodes, it deposits on the cathode, with a purity up to 99.99 %, where it is extracted
and recast.
The facilities for a low grade copper (less than 80 % copper) need to have in addition
a converter step and fire-refining to obtain high grade recycled copper. Further
processes may include alloying with other metals.
Aluminium Smelting
Aluminium smelting takes place primarily in reverberatory furnaces, but also in tower,
rotary and sweating furnaces. Usually these recovery facilities use batch processing in
melting and refining operations. The aluminium fraction is mostly remelted under the
addition of fluxing salts to prevent oxidation in a temperature range from 585C 650C depending on the amount of alloying elements.
The induction smelting and refining process is designed to produce aluminium alloys
with increased strength and hardness by blending aluminium and hardening agents in
electrical induction furnace. The process include charging scrap, melting, adding and
blending the hardening agent, skimming, pouring and casting into notched bars.
Hardening agents include manganese and silicon [EPA 1995].
Zinc Smelting
Zinc scrap is processed by selective smelting in rotary, crucible, reverberatory, and

electrical induction furnaces. Flux is used in these furnaces to trap impurities from the
molten zinc. The impurities float to the surface of the melt and dross, and is
subsequently skimmed from the surface while the remaining molten zinc is poured
into molds or transferred to the refining operation in an molten state [EPA 1995]. A
sweating furnace slowly heats the scrap containing zinc and other metals to
approximately 364 C. This temperature is sufficient to melt zinc but is still below the
melting point of the remaining metals [Rosseau 1991]. Molten zinc collects at the
bottom of the furnace and is subsequently recovered. The zinc alloys produced from
pre-treated scrap during sweating and melting processes may contain small amounts
of other metals like copper, aluminium, magnesium, lead or others present in the
mixture.
Lead Smelting
Lead scrap with Zinc and other metals may be extracted from the heavy fraction by
selective smelting. In a selective smelting lead is the first metal smelted at 350 C. In
a second furnace zinc is smelted at 425 C and the remaining copper rich fraction with
precious metals is further separated in a copper smelter [Dalmijn, Witteveen 1991].
Magnesium Smelting
Magnesium scrap is sorted and charged into a steel crucible furnace maintained at
approx. 675 C. To control oxidation of the melt fluxes of chloride salts, magnesium,
barium, magnesium oxides and calcium fluorides must be added. This fluxes float on
the melt preventing air contact. The composition of the melt must be carefully
monitored, once the molten metal reaches the desired levels of key components, it is
poured, pumped, or ladled into ingots.
Iron and Steel Smelting
The two basic types of furnace used in steel making and recycling are the electric arc
furnace, and the basic oxygen furnace. While the electric arc furnace is almost entirely
designed to operate on steel scrap, the oxygen furnace is able to use only 20 to 30 %
of the melt capacity of steel scrap. The remaining 70 % to 80 % consists of molten pig
iron which is used in a blast furnace from iron ore, limestone and coke.
2.4.1.2Hydrometallurgical Processes
The hydrometallurgical recycling is characterised as a multistage process where
acquired metals are dissoluted and recovered by methods like electrolysis, extraction,

cementation, ion-exchange or precipitation. Therefore hydrometallurgical processes

are also named under wet-chemical processes.

Figure 64: Overview of the main hydrometallurgical recovery methods

[Modified from http://147.96.1.15/info/metal/qprep.htm]
Compared to pyrometallurgical processes it uses much less energy. Its industrial scale
is more than 10 times smaller than the conventional pyrometallurgical smelter plants.
Dissolution
After a thermal and mechanical treatment, the metals are dissolved at pressurised
vessels using water, oxygen and other substances at ambient temperature. The
objective of the leaching process in the recycling process is to produce a metal from
impure metal or metal compounds, which have been prepared by a pyrometallurgical
process. The leaching process can be performed by two methods: the heap leaching
and the agitation leaching.
In the heap leaching process the solids are brought in contact to the leaching solution
by pumping or evenly spraying the solution over the top of the heap [Boyer, Gall
1985]. As the solution percolates through the heap it dissolves the metal. The agitation
is either performed by bubble action using compressed air or mechanical movement
using impellers. The standard equipment is the Pachuca tank. Through a central pipe
an air lift pushes the solution in an upward direction increasing the contact of solids to
the leaching solution. The maintenance and operating costs are lower then for
mechanically working agitators.
For mechanically working agitating tanks the main difference is the type of impeller,
depending on the flow pattern by the type of tank. The major types of impellers used
are marine propellers, paddles and turbines. Here pressure leaching has the objective
to decrease the dissolution time of metals by permitting higher operating
temperatures. This supports the solubility of oxygen and further the rapid oxidation of
metals. The standard equipment used for pressurised metal leaching is the autoclave
(see Figure 65). They are made out of metal for strength and often are of stainless
steel or titanium because of severe corrosion that can occur at high pressure and high
temperatures. Most autoclaves have agitators for mixing combined with heating and
cooling coils for temperature control of the process.

The schematic below shows the components of a horizontal acid leach autoclave:

Figure 65: Illustration of an autoclave for metal dissolution

(1.Motor Drive Assembly for Agitator, 2. Compartment Divider, 3. Agitator Shaft, 4.
Service Nozzle, 5. Support Saddle, 6. Carbon Steel Shell/Lead and Brick Lined )
The process of the selective dissolution of silver, platinum and base metals by nitric
acid is still used today. It was temporarily substituted by sulfuric acid, but because of
the costly equipment and considerable off-gas problems it changed back again.
(Me)solid + 2 HNO3 + O2 Me(NO3)2 dissoluted + H2O
Not only the high consumption of expensive and complex reagents also the disposal
of the non-metallic fraction and the treatment of solvents and sludges are concern of
hydrometallurgical processes.
Recent research focus on a single dissolution stage, which excludes interstage
pollution and contamination problems [Goosey, Kellner 2002]. Here various metals
are dissoluted at once, with highly concentrates of HCl + NaCl electrolytes (ph1).
Chlorine is leaching metals of electronic scrap via oxidative dissolution and produces
a de-metallised waste:
2CL- 2Cl + 2 eMscrap + Cl - MCl -

MCl- M+ +Cl
Dissolution of Gold
The recovery of gold containing compartments of PCBs are whether edge connectors
or gold coated assemblies (edge, pin connectors) from manually separated scrap
boards. Gold is separated as a metal flake via the acidic dissolution of copper
substrates or the dissolution of gold in cyanide/thiourea based leachants:
2 Au + 4NaCN + O2 + 2H2O 2 Na[Au(CN)2] + H2O2 + 2NaOH
Conventional methods for gold and silver recovery are based on the dissolution in
cyanide leaching media over the entire pH range [Reprints, 1991]. The fine grinded
gold is dissolved by sodium cyanide or calcium cyanide which then reacts under
oxygen and lead to a cyano-complex. To increase the velocity of the solubility Lurgi
proposed a process where the operation is put under pressure of 40 bar where the
reaction time is reduced to 2 h [Rousseau 1991]. To fasten the reaction even more an
additional oxygen donor, such as hydrogen peroxide is added. These reaction
processes are efficient within a pH range of 10 and 12 and in the presence of catalysts
as Fe(III) and Cu(II), which enable the decomposition of hydrogen peroxide and
consequently the oxidation of cyanide (CN 2-) to cyanate (CN4+).
The gold recovery takes place by precipitation or electrolysis. It can also be extracted
from solutions with a very low gold content ( 0,1 g/L) by ion exchange resins or
activated charcoal extraction [Habashi 1997].
Ion Exchange
The ion-exchange process involves an adsorption and an elution process in an ionexchange column. Its aim is whether to separate selectively dissolved metals or
concentrate metals.
In the adsorption process metal-ions are removed from an aqueous solution while
passed through a bed of resins. These resins can be cationic or anionic. The cathodic
resins are strong or weak acids, which exchange H + ions. Anionic resins are strong or
weak basis. Here mostly Cl- ions are exchanged with anions in solution [Boyer, Gall
1985]. The phenomena of the affinity of the resins towards specific metal ions realise
the selection of specific metal ions from a complex solution.
For the recovery of copper, nickel and lead sodium-based resins weak-acid chelated
resins are applied. The metal ions are captured by the resins and backwashes with an

acid solution, which supplies hydrogen ions and exchanges with the metal ions and
returns as metal salts in a acid holding tank.
In the REMCO metal recovery process ion exchange (MRIX) process 10 gallons of
solution per cubic feet of resin is produced (ca. 1,400 litre per cubic meter resin)
[http://www.remco.com/ix-procs.htm]. Some metal salts are easily removed by
evaporation (sodium forms of cyanide and chromium, sulphate or chloride salts of
copper and nickel), for metals as copper, nickel, zinc it is better to recover by
electroplating. To prepare the column for the next operation a thorough fresh water
rinse is arranged and a solution of 5 % sodium hydroxide is passed through the
column to replace the hydroxide ions with sodium ions. A second backwash is
generated to remove the remaining caustic soda. The generation cycle takes about 3-5
h.
The ion-exchange plant require high capital costs and a large plant area, because of
the large amounts of input material and enhanced process technology [Boyer, Gall
1985]. Ion exchange system are able to recover from a concentration of 10-50 ppb.
Extraction
The extraction of metals is a method to prepare the process products of preceding
treatments (decomposition) for following procedures (electrolysis). It is a chemical
process which selectively exchanges metal species between an impure feed solution
and a pure aqueous feed solution. The metal dissolves in an organic solution and is
stripped from the organic solution (alcohol, ethers, ketones etc.) by an aqueous
solution. One objective is to separate the desired precious metals from interfering
components. A complete extraction of a metal is normally not to achieve. A small
fraction of precious metals always remains with the base metals and cannot be
recovered. But to deduce the loss, the process can be arranged reversibly.
Carbon Adsorption
The use of the carbon adsorption process is exclusively to recover noble metals as
gold and silver. At low temperatures the metals deposit in metallic form on the carbon.
The metal leaching solution is fed to carbon columns and almost completely removed
from the solution by adsorption on the solid carbon. When the carbon is loaded the
metals are stripped, which can be done by passing a stripping solution over the
column. The stripping is followed by electrowinning from solution of a very pure gold
or silver product.
Electrolysis

The aim of the electrolysis is the decomposition of a metal solution by a supplied

current on two poles. The ions are neutralised when transferred to the different
charged poles. At the cathode positive valued metal ions are separated from other ions
moving into the direction of the anode.
A recently developed method with resulting low capital and operation costs for the
recovery of copper and zinc is the application of an slurry electrolysis cell. The
electrolytic reaction initiated through an applied current (1.25-1.75 V) in an
electrolytic cell leads to a redox-reaction. In the electrolysis oxygen and hydrogen is
produced at the anode, initiating the leaching of copper/zinc from the cathode and
producing acid.
This process is however only possible if a mixing is avoided through the separation
electrolyser cell [Habashi 1997]. A mixing reaction is avoided by a membrane,
inhibiting the transport of large metal ions. The electrolyser cell contains anode
compartments, a cell separator on either side of the anode chamber and a cathodic
compartment as illustrated in the following figure.

Figure 66: Scheme of an electrolysis cell

Anodic reaction
1.
In base electrolyte: 4 OH - O2 + 2 H 2O + 4 e
2.
in acid electrolyte: 2 H2O O2 + 4 H + + 4 e
Cathodic reaction
Me n+ + ne - Me
Nickel can be recovered electrolytically to give pure nickel powder. The electrolyte
has to be refreshed continuously and includes also stabilisator and buffer substances
[Nickel, 1996]. The anolyte solution is a NaOH solution of a pH>6 [Rousseau 1991].
At the anode chloride ions are oxidising to sodium hypochlorite and nickel is
recovered from the solution by electro- deposition as a counter reaction for the
chlorine generation at the cathode.
The precious metals gold, silver, platinium and palladium are recovered by this
method. Precious metals are easier to separate from solvents than unprecious ones,
because of the higher affinity to anions. It was observed that the metals Ag, Pd, Au,
Cu, Pb, Sn of one solution can be selectively recovered under the application of
varying decomposition potentials [Goosey/Kellner 2002].
Electro-refining
Metals as copper, lead and nickel, which are recovered from smelters in a purity from
90 98.5 % are refined by electrolysis. The refinement of copper takes place in an
electrolysis cell, where copper anodes, produced by pyrometallurgical processes are
dissoluted and recovered at the cathode with a purity of 99.9%.
Impurities in the copper anode include lead, zinc, nickel, arsenic, selenium, tellurium,

and several precious metals including gold and silver. Potentiostatic control is
essential to prevent the dissolution of silver and disposition at the copper cathode. So
that less active metals like the precious metals silver, gold, platin, palladium are not
oxidised at the anode, but aggregated at the bottom of the electrolysis cell and
recovered by several treatment processes. Nickel impurities of the copper fraction are
dissoluted in the solvent.
Depending on the metal being plated different cathode materials can be used. For
copper electrowinning titanium, stainless steel and copper itself (see Figure 67) can be
used [Boyer, Gall 1985]. Aluminium is used to recover zinc and titanium, and
stainless steel has been used to recover manganese and cobalt.
The electrolyte consists of an acidic solution of CuSO 4. Application of a suitable
voltage to the electrodes causes oxidation of copper metal at the anode and reduction
of Cu2+ to form copper metal at the cathode. This strategy can be used because copper
is both oxidised and reduced more readily than water.

Figure 67: Electrolysis cell for refining of copper. As the anodes dissolves, the
cathodes is grown in size on which the pure metal is deposited.
[http://cwx.prenhall.com/bookbind/pubbooks/blb/chapter23/medialib/blb2304.html]

Once the metal has been deposited on the cathode it must be recovered. This usually
involves peeling the plated metal away from the cathode.
Cementation
Cementation is a type of precipitation method implying an electrochemical
mechanism. The tendency of one metal to displace or reduce another metal from
solution is based on the potential of metals for reduction. A more electropositive metal
will tend to reduce a less electropositive metal from solution (e.g. zinc will tend to
reduce a less active or noble metal as silver or copper). The greater the difference in
potential between the two metals the more complete will the reaction be. The rate at
which cementation reactions occur depend on initial concentrations, temperature,
agitation, polarisation, metal characteristics and agents [Boyer, Gall 1985]. An
example of cementation at industrial scale is the copper reduction by metallic iron.
However, the noble metals (Ag, Au and Pd), as well as As, Cd, Ga, Pb, Sb and Sn, can
also be recovered in this way.
Copper
Copper cementation is a procedure where a more noble metal can be extracted with a
less noble metal (e.g. iron, aluminium or Fe-Al alloys). The positioning of a less noble
metal iron leads to the deposition of a more noble metal like copper in form of sludge.
This occurs through the exchange of their charge, the electrons switch to the copper:
CuSO4 + Fe2 FeSO4 + Cu
Cu 2+ + 2 e- Cu
Fe Fe 2+ +2eConcentrates produced vary from about 65 to 95 per cent copper according to the
procedures used. Copper sulphates are fed to open launders or cones containing steel
scrap, where copper is recovered at the bottom.
Gold

Another cementation process is the recovery of gold through the copper cementation
of gold thiosulphate with the use of alkaline thiosulphate solution [Choo, Jeffrey
2004]. This involves the dissolution of the substrate metal, and the simultaneous
reduction and deposition of gold from the solution. During the cementation of gold on
copper, the gold thio-sulphate is reduced to gold metal. Cementation of Cu/Au occurs
according to the following stoichiometry:
Au (S2O3)23- + S2O32- + Cu Cu (S2O3)35- + Au
The presence of copper in these solutions introduces the problem of co-precipitation
of copper during gold recovery. However, cementation offers a means of getting
around this, simply by selecting an appropriate substrate metal. Of these substrates,
copper is among the most promising, as the copper that goes into solution during
cementation could be oxidised to Cu(II), which is the oxidant during the leaching
process.
Precipitation
The removal of ionic species from a solution as solid compounds is described by the
precipitation process. Precipitation can be used for the removal of impurities and
concentration of the metal compound, e.g. the recovery of sulfides of nickel, copper,
lead and zinc form leaching solutions. The treatment costs are low and solutions with
very low concentrations of metal values can be treated.
The precipitation methods can be described by:
1. Addition of chemicals (appropriate cation or anion)
2. Changing of the pH value
(as the OH- value increases, the solution becomes more basic, solid hydroxides
precipitate (iron, copper, cobalt, nickel are precipitated selectively as hydroxides in
solutions by raising the pH with mild and lime)
3. Evaporation of water from the solution

Gaseous Reduction
Also reducing gases as hydrogen, carbon monoxide and sulphur dioxide can be used
to reduce metals from an aqueous solution. Hydrogen is among the most widely used,
because of simple reaction products. Using higher pressures of hydrogen gas and
higher temperatures in an autoclave nickel is reduced from solution according to the
following chemical reaction:
Ni2+ + H2 Ni + H +