Electrometallurgy

II. ELECTROMETALLURGY
 Pengantar elektrometalurgi
• Electrolytic processing is used commercially to
recover and/or refine metals that include large
scale production for metals such as aluminum,
copper, magnesium, nickel, and zinc as well as
small scale production for metals such as gold
and silver.
• There are also new and exciting opportunities
to utilize electrometallurgy in the production
of titanium, lead, and other metals.
 Pengantar elektrometalurgi
• Electrolytic processing of metals involves
common challenges:
– Energy is an important issue in electrometallurgy.
– Other important areas of interest are chemistry,
productivity, and safety.
 Electrometallurgy
• Electrometallurgy deals with the use of electrical
energy for production of pure metals by electrolysis.
• Electrometallurgy is usually the last stage in metal
production after corresponding pyro-or
hydrometallurgical operations.
• The process within the metal is produced by its
aqueous salt as a last stage of the hydrometallurgical
operations, is known as electrowining.
• Electrolytic purification of the crude metal produced by
pyrometallurgical operations is known as
electrorefination.
 Electrometallurgy

• Both processes are based on electrolysis, i.e. on the

process in which forced electrons exchange of the
matter occurs.
• Electrolysis, in some cases, is an irreplaceable way for
production or refination of some metals. For example,
aluminum can not be produced by pyrometallurgical
procedure.
• Electrorefination of metals is unique process
considering the level of metal purity, energy
consumption as well as possibility for extraction of
precious metal.
 Electrolytes
• Acids
• Bases
• Alkalis
• Salts
 Electrolytes
• Acids characteristics:
– Turn blue litmus red
– Neutralize bases
– React with active metals with the evolution of
hydrogen
– Possesses a sour taste.
• Basis Characteristics:
– Turns red litmus blue
– Neutralize acids
– Tastes offensive
– Gives a soapy feel
 Electrolytes- acids
• Mineral acids: acids derived from mineral
substances, e.g. Hydrochloric acid which is
obtained from common salts, nitric acid from
sodium or potasium nitrate, sulfuric acid from
sulfur, phosporic acid from calcium phosphate
etc.
• Organic acids: acids which contain carbon as
essential elements and are obtained from either
plants or animal for ex., formic acid (HCOOH),
acetic acid (CH3COOH)
 Electrolytes- acids
Acid yielding Oxy-acids
elements “ic”- acid “ous” acid “hypo” acid “per” acid
Sulfur H2SO4 H2SO3 H2S2O3 H2S2O8
Sulfuric Sulfurous Hyposulfurous persulfuric
Nitrogen HNO3 HNO2 H2N2O2
Nitric Nitrous Hyponitrous
Chlorine HClO HClO2 HOCl HClO4
Chloric Chlorous Hypochlorous perchloric
Phosporous H3PO4 H3PO3 H3PO2
phosphoric phosphorous hypophosphorous
 Electrolytes- acids
• Monobasic acids: acids whose molecules
contain only one replaceable hydrogen atom,
for ex. HCl, HNO3, HClO3
• Dibasic acids: acids whose molecules contain
two replaceable hydrogen atoms in each
molecules for ex. H2SO4, H2SO3, H2CO3 etc.
• Tribasic acids acids which have three
replaceable hydrogen atoms in each molecul
for ex. H3PO4
 Electrolytes-Basis
• Substances which yields hydroxy ions as the
only negative ion, when dissolved in an
ionizing solvent (usually water).
• The activity of bases :
– Monoacid bases: NaOH, KOH
– Diacid bases: Ca (OH)2, Mg(OH)2
– Triacid bases: Al(OH)3, Fe(OH)3
 Electrolytes-Alkalis
• Hydroxides:
– KOH, potassium hydroxide (caustic potash)
– NaOH, sodium hydroxide (caustic soda)
– Ca(OH)2, calcium hydroxide (slaked lime)
• Non hydroxide:
– Ammonia
• Salts:
– NaF3
– NaCl
– dll
 Electrolytes-Salts
• NAF3
• NaCl
 Electrochemical cell
• Galvanic cell
• Electrolytic cell
 Sel elektrolisa
• Basic consisting elements of the
electrolytic cell are shown in the
simplified scheme in Figure 1.
• Two electronic conductors –
electrodes (anode and cathode),
an ionic conductor (electrolyte)
and an energy source (battery) are
necessary to perform electrolysis.
• In the electrolysis cell electrode
reactions are non-spontaneous,
i.e. they are forced by an external
source of energy. So, reduction of
the metal ions to pure metal
(production or refination of metal)
is enabled.
 Sel elektrolisa
• For efficient electrolysis, the above elements have to satisfy some
criteria. So, electrodes have to:
– be made by an appropriate material that promotes
corresponding electrode reactions and exhibits good long-term
stability and is environmental friendly;

– be appropriately processed in order to remove electrode products

easily. Cathodic edges should be rounded off to prevent dendritic
growth;

– be appropriately arranged into the cell for better volume efficiency.

The shorter cathode-anode distance, the lower the Ohmic drop in the
cell and consequently the lower energy consumption. On the other
side, grown deposit on the cathode may cause short cut if the
electrodes are too close.
 Sel elektrolisa
•
• The electrolyte should contain:
– compound of the ion – participant in the electrode reaction;
– compounds that provide optimal electrical conductivity,
corresponding acidity/ alkality and/or complex forming ability;
– corresponding additives for regulation of the surface tension, to
optimize the diffusion potential, to provide better adhesion of the deposit
over the cathodic substrate, to reach better optical and mechanical properties
of the deposit;
– in some cases – mechanical components, e.g. thin oil layer or inert
plastic balls in order to reduce electrolyte evaporation;
- - additives for optimizing density and viscosity in the case of the
molten salt electrolysis.
 Sel elektrolisa
• The source of energy should be:
• – properly designed to provide voltage and current output high enough for
performing electrolysis;
• – equipped with voltage regulation system;
• – long-term stable.

• The electrolysis cell has to be:

• – prepared by a material having good chemical, thermal and mechanical
stability. Traditional materials are wood, glass, concrete, stainless
metals/alloys, while the recent ones are various polymer materials or
coatings;
• – equipped to shoulder electrodes (whose weight can reach even tens of
tones) and to supply them with electricity;
• – equipped for heating/cooling, stirring/ circulation and filling/emptying
the electrolyte;
Electrorefination vs Electrowinning
• Depending on the input materials in the cell, electrolysis is aimed to
produce or refine the metals.

• In the case of electrorefination, anodes are prepared by a raw metal

produced by pyrometallurgical process. So, the basic metal ions originate
by dissolving of the anode and further, they reduce on the cathode where
the final product is highly-pure metal. In this case, there are soluble
anodes which are the main source of basic metal ions, while the
electrolyte possesses basic metal ions in quantity only to maintain
sufficient concentration to avoid deposition of impurities on the cathode.

• In the case of electrowining the source of basic metal ions is the

electrolyte. The anode does not dissolve during this process. On the anode
some other anodic reaction occurs, e.g. oxygen or chlorine evolution. For
this reason they are called non-soluble anodes.
Fig. 2. Simplified schemes of
electrorefination and
electrowining processes78
Perica Paunović Maced. J.
Chem. Chem. Eng. 30 (2), 75–
83 (2011)
 Electrowinning-Electrorefining
• To produce purer and more compact metallic
product, it is necessary to provide:
• – better quality and arrangement of the electrodes.
The purest deposit can be produced if electrodes are
arranged vertically and maintain constant optimal
distance between anode and cathode;
• – optimal composition of the electrolyte to maintain
both continuous constant supplying the cathodes
with basic metal ions and low concentration of
impurity metal ions.
 Electrorefining
• In the case of electrorefining, purification of the electrolyte
should be performed in order to reduce the concentration of
impurities and to avoid their deposition on the cathodic
product.
• - The concentration of the acid (mostly sulfuric acid) should be
high enough to provide high electrical conductivity, i.e. lower
Ohmic drop of the electrolyte. In order to smooth the metal
deposit and to control the crystal growth, corresponding
additives are used, e.g. gelatin as deposit smoother or
thiourea and chloride ions as crystal growth regulators;
• –
 Electrowinning-Electrorefining
• optimal temperature.
– Heating the electrolyte causes higher electric conductivity and
consequently lower energy consumption. Also, the solubility of the
basic metal ions is higher and consequently their diffusion to the
cathode is made easier, as well as the rate of the charge transfer on
the cathode is higher.
– At higher temperatures electrolyte density and viscosity decrease that
is suitable for avoiding particles of anode mud to be included into the
cathodic product. But, the working temperature should have optimal
value (not so high) due to evaporation of the electrolyte and higher
energy consumption.
– In the case of electrowining of electronegative metals such as Zn, In or
Cd, overpotential of hydrogen evolution on the cathode is made
easier. The presence of hydrogen is very harmful for the cathodic
product;
• –
 Electrowinning-Electrorefining
• optimal current density.
– At higher current density, electrodeposition is
faster (desirable), but the dendritic growth is
forced (undesirable).
– Dendritic deposits enslave electrolyte and anode
mud particles more easily. Also, dendritic
structure of metals is technically non-applicable.
 Aqueous Electrolysis
• Electrolysis in aqueous electrolytes is a suitable process for metal
production and refination at low temperature. As a result, cost-
effective metal of high purity can be produced. The main solvent of
the electrolytes for electrolysis is the water. There is not other
solvent in electrochemistry that possesses unique water properties,
such as:
• – polarity – prerequisite for dissolving ionic compounds,
• – electrolytic dissociation – prerequisite for better electric (ionic)
conductivity of the electrolyte,
• – stability (physical, chemical and thermal),
• – wide interval of liquid state existence,
• – non-toxic, non-corrosive and non-complexable,
• – availability and
• – inexpensive.
 Molten salt electrolysis
• But, electrolysis in aqueous electrolytes is limited to metals more positive
than hydrogen such as Cu, Ag, Au, and more negative ones that have high
overpotential for hydrogen evolution such as Zn, Cd, In etc.
• The apparent electronegative metals such as Na, Mg, Al, K, Li can not be
produced by electrolysis in aqueous solution because on the cathode only
hydrogen evolution occurs.
• In order to reduce these metals on the cathode, H+ ions have to be
removed from the electrolyte, i.e. have to find other solvent which have
above characteristics.
• Unfortunately, there is not some other inorganic or organic solvent with
corresponding properties in industrial practice. So, the other approach to
solve this problem is using molten metal salts.
• This is still a unique way for production of alkaline and alkaline earth
metals (Na, K, Mg) and Al. Their oxides are very stable and their
pyrometallurgical production is technically and commercially non-
effective.
 Molten salt electrolysis
• Molten salt electrolysis has more disadvantages related to
the aqueous electrolysis, such as:
• – considerably higher working temperatures (up to 900 oC
in case of Al),
• – complex composition of the electrolytes,
• – highly-aggressive electrolytes,
• – complex electrode reactions,
• – low current efficiency, i.e. high specific energy
consumption and
• – anodic effect – (stop of the current pass along with high
rise of overvoltage, which causes breaking off of the
electrolysis process.
Daur Hidup aluminium
SEJARAH PEMURNIAN ALUMINIUM
Sejarah perkembangan Al
In 1807, Sir Humphrey Davy, the
British scientist, postulated the
existence of the element
arguing that alum was the salt
of an unknown metal which he
said should be
called "Alumium".

The name was respelt as the

more euphonious aluminium by
later scientists.
Awal perkembangan
• In 1886, Charles Martin
Hall and Paul L.T. Héroult
each perfected a similar
method for producing
aluminium lectrolytically
from aluminium oxide
(alumina) dissolved in
cryolite.

• Hall filed patents in the

USA and Héroult in
France, a fact that was
to have great influence
on the future structure
of the industry.
Perbandingan harga proses
• The success of the Hall/Héroult
process was compounded in 1888
when Karl Bayer, an Austrian,
developed a viable process for
producing alumina from bauxite
ore. While the Deville production
cost savings were the more
dramatic in magnitude, the final
figure (price) was still
uncompetitive with alternative
materials.

• The Hall/Héroult invention closed

the critical gap. By 1890 the cost of
aluminium had tumbled some 80
percent from Deville's prices (see
Figure 1101.01.04). The metal was
now a commercial proposition,
how would it be used?
Bauxit dan Bayer
BAUXITE
 Bauxite di Indonesia
• Tembeling, Pulau Bintan, Riau
• Tayan, Kalimantan Barat

© John Veevaert
Gibbsite and Boehmite
 Mineral bauxite
Unit Gibbsite Böhmite Diaspore
Composition Al(OH)3 AlO(OH) AlO(OH)
Maximum Alumina
% 65.4 85.0 85.0
Content

Crystal System Monoclinic Orthorhombic Orthorhombic

Density gcm-3 2.42 3.01 3.44

Temp. for Rapid
°C 150 350 450
Dehydration

Bauxite occurs in three main forms depending on both the number of molecules of
water of hydration and the crystalline structure. The three structural forms of bauxite are
Gibbsite, Böhmite and Diaspore.
mineralogi bauxite (1)
mineralogi bauxite (2)
 mineralogi bauxite (3)
• These mineral phases are either active (caustic
soluble) or inert (caustic insoluble) under low-
temperature digestion (LTD) conditions (100–
150∞C).
• However, under high-temperature digestion
(HTD) conditions (235–260∞C), bearing other
incentives, all these phases, except rutile, are
attacked by caustic.
PROSES BAYER
Proses Bayer
 Proses Bayer
Step 1 - Mixing: Crushed and Mixed with Caustic
Soda, bauxite is pumped into huge digesters.

Step 2 - Digestion: Under high pressure and heat, the

caustic soda dissolves the Alumina, or Aluminum
Oxide, in the bauxite to form Sodium Aluminate.

Step 3 - Clarification: While the Sodium Aluminate

remains in the solution, iron oxides and other solid
impurities drop to the bottom of the settling tank,
where, as red mud, they are pumped to a disposal
pond.

Step 4 - Precipitation: After the Sodium Aluminate is

further cooled, it is agitated and seeded with
Aluminum Hydroxide crystals. These form larger
crystals, which gradually settle out of the solution.
Seed crystals and Sodium Aluminate remaining in the
solution are then recirculated.

Step 5 - Calcination: The Aluminum Hydroxide

crystals are roasted at more than 1800 degrees F to
remove the water. A fine white powder, Alumina,
remains half aluminum and half oxygen. It is then
ready for transport to a smelter.
 Proses Bayer
• Bauxite, the most important ore of aluminium, contains only 30–54% alumina, Al2O3, the rest
being a mixture of silica, various iron oxides, and titanium dioxide.

• The alumina must be purified before it can be refined to aluminium metal. In the Bayer
process, bauxite is digested by washing with a hot solution of sodium hydroxide, NaOH, at
175 °C. This converts the alumina to aluminium hydroxide, Al(OH)3, which dissolves in the
hydroxide solution according to the chemical equation:

Al2O3 + 2 OH− + 3 H2O → 2 [Al(OH)4]−

• The other components of bauxite do not dissolve. The solution is clarified by filtering off the
solid impurities. The mixture of solid impurities is called red mud, and presents a disposal
problem. Next, the hydroxide solution is cooled, and the dissolved aluminium hydroxide
precipitates as a white, fluffy solid. Then, when heated to 1050°C (calcined), the aluminium
hydroxide decomposes to alumina, giving off water vapor in the process:

2 Al(OH)3 → Al2O3 + 3 H2O

Bayer refinery
(Ref.: W.E. Houpin, Journal of Chemical Education, v. 60, n. 4, 1983: 279-
282)

ELEKTROKIMIA PEMURNIAN
ALUMINIUM
 Aluminium
• Aluminum Electrowinning
• The aluminum industry has evolved to its current position of
approximately 41 million tonnesannual worldwide primary
production produced in over 45 countries.
• This production is concentrated in around 20 major aluminum
metal producing companies who account for up to 65% of this
metal production. Most of these operations use alumina
derived from bauxite.
• Both low and high silica bauxite are refined using the Bayer
Process and the product is alumina powder which is then
electrolytically reduced to aluminum metal by the Hall-
Heroult process.
• There have been many advances made in the Hall-Heroult
production process which haveresulted in significant
improvements in productivity, energy efficiency and its
impact on the environment.
• However, the process used today that is based on a
consuming carbon anode, a 5 cathode metal pool and
fluoride based electrolyte is fundamentally the same as the
process originally developed by Charles Hall and Paul
Héroult 125 years ago.
 Sel elektroda
• There are two types of electrochemical cells or pots in use
today. The Soderberg Cell (both the horizontal stud (HSS)
and vertical stud (VSS) versions) is based on a continuous
anode that is made from carbon paste that is fed to the cell
and baked in-situ.
• This cell technology accounts for around 10% of the world
Al production. The other type of cell technology, the Pre-
bake (PB) Cell is based on multiple anodes that are made
from coke and pitch which are formed and baked in
furnaces outside of the cell accounts for the rest of the
metal production.
• Schematic cross sections of both the Soderberg (HSS and
VSS) and modern Pre-bake cells are shown in Figure 1.
Sel Elektroda
Elektrolit
 Reaksi Elektroda
Katoda Anoda
Efek Anoda: Pembentukan gas CO2
Efisiensi Arus
Voltase Sel
 Titanium

Metalurgi Ekstraksi
Aplikasi
 Mineral

Rutile (TiO2) dalam quartz Rutile (TiO2) dalam hematite

 Proses pembuatan logam Ti
• Hunter process
• Kroll process
• Electrochemical process
• FFC Cambridge process
Proses Kroll

Konversi Rutile (TiO2) menjadi Ti

spons melalui tahap berikut:

1) Melewatkan gas Cl2 pada bijih,

menghasilkan TiCl4 tidak berwarna.
2) TiCl4 dimurnikan dengan distilasi
fraksi
3) Liquid TiCl4 direaksikan dengan Mg
atau Na dalam kondisi atmosfer
inert (Ar) untuk mendapatkan Ti
spons, sedangkan Mg dan Na
didaur ulang.
 Ti spons

(http://www.toho-titanium.co.jp/en/products/sponge_en.html)
 Preparasi TiCl4
• Ilmenite (FeO.TiO2) diproses untuk menghasilkan ferrotitanium melalui
peleburan reduksi dengan komposisi: Ti: 18%; Al: 5-8%; Si: 3.5-6%; Cu
3-4%.
• Peleburan reduksi Ilmenite pada dapur listrik menghasilkan:
– Besi tuang titanium
– Terak dengan kandunagn TiO2 70-80% → bahan baku titanium klorida.
• Reaksi yg terjadi selama klorinasi:
– TiO2 + 2Cl2 + C → TiCl4 + CO2
– TiO2 + 2 Cl2 + 2C →TiCl4 + 2 CO
– TiO2 + 4 Cl2 + 2C → TiCl4 + 2 COCl2
Preparasi TiCl4-proses klorinasi
Kondensasi klorida
Pemurnian TICl4
 Pemurnian TiCl4 dengan distilasi fraksi

TiCl4 (Tm= 136 oC)dipisahkan dari:

-FeCl3 (319oC)
-VCl4 (164oC)
-VOCl3 (127oC)
-SiCl4 (57oC)
 Kroll process
• TiCl4 + Mg → Ti + MgCl2 (Kroll process)
Dikenal sebagai magnesiothermic process
• TiCl4 + Na → Ti + NaCl (Hunter process)
Proses kontinu dibanding kroll process
Reduksi TiCl4
Reduksi dengan Mg
Proses perolehan Ti spons
 FFC Cambridge process
FFC: Fray-Fathing-Chen (nama-nama para peneliti di Univ. Cambridge)

(George Zheng Chen, Derek J. Fray & Tom W. Farthing, Nature 407 (2000) p. 362-363)
 Alat uji FFC Cambridge process

Reaksi Katoda:

a. Pengendapan kalsium
Ca2+ + 2e- = Ca
TiOx + x Ca = Ti + xCaO

(pada potensial lebih katodik)

b. Ionisasi oksigen
TiOx + 2xe- = Ti + 2xO-

(pada potensial kurang katodik)

Reaksi anoda:

2xO- = O2 + 2xe-
FFC Cambridges
 FFC-cambridge Process - produk

Gambar SEM reduksi serbuk TiO2

menjadi logam Ti.

(a) Gambar SEM struktur mikro

dalam sebuah pellet dan disinter
850oC, 48 jam. Kemurnian
99.9%

(b) Setelah direduksi pada 3.2 V,

950oC, 12 jam, Argon, anoda
karbon.
Proses reduksi TiO2 dengan fasa gas
Proses reduksi TiO2 dengan pre-form -
sellulosa