Flowsheets
✓ The common metals, namely copper, lead, zinc, nickel, tin,
aluminum, and so on produced in bulk are refined by
different methods based on the difference in physical and
chemical characteristics of the metal and impurities.
✓ During refining of high reactive metals such as uranium,
thorium, titanium, and zirconium, it is beneficial to eliminate
those impurities associated with the ore right in the
beginning.
✓ In processing reactive metals, the compound obtained from
the ore breakdown step is purified by chemical separation
techniques like selective distillation (titanium), chemical
precipitation (uranium), ion exchange (uranium, zirconium),
and solvent extraction (uranium, thorium, zirconium etc.).
✓ Thermodynamically, the pure phase is unstable. It has an
inherent tendency to pick up impurities from the surrounding
environment because free energy of the pure phase is lowered by
absorption of impurities. Hence, purification becomes more and
more difficult as we approach the pure state because the purer
phase is more prone to picking impurities.
✓ Knowledge of thermodynamics and kinetics are of utmost
importance for generating favorable conditions in all refining
techniques. It is more difficult to remove impurities held at lower
chemical potential.
✓ During refining, the impure metal is brought into contact with
slag or vacuum, which can pick impurities at lower chemical
potential. Hence, knowledge about activities of the metal and
impurities would be helpful in formulating thermodynamic
conditions for refining by a particular technique.
✓ Since chemical potential decreases with decrease in the
concentration of the impurity it becomes more and more difficult
to achieve 100% pure metal. Thermodynamically, a metal with
several impurities needs to be treated as a multicomponent
solution, which requires adequate knowledge of interaction
coefficients.
✓ Difference in physical and chemical characteristics of the metal
and the impurities are made use of in various refining processes.
For example, a large difference in the extent of affinities of
different metals for oxygen is employed in refining steel, copper,
and lead bullion.
All the refining methods are classified into four main groups:
1. Metal-slag processes: In these processes the less noble metal is oxidized and slagged off. This is commonly known as fire refining. Removal of
carbon, silicon, manganese, and phosphorus from pig iron during steelmaking falls under this category. Copper from lead, bismuth, and tin can be
removed by treating the crude with sulfur. Similarly, chlorination is useful in eliminating zinc from lead; zinc, copper and lead from bismuth; lead
from tin; and silver, copper, and zinc from gold.
2.Metal-metal Processes: Liquation and zone refining are the important examples in this group. Zone refining is used for ultra-purification of
some metals.
3. Metal-gas processes: Under this category, distillation, vacuum treatment, carbonyl decomposition, disproportionate reaction, and iodide
decomposition form important examples. Disproportionate reaction and iodide decomposition techniques are employed for ultra-purification of
reactive metals.
4. Miscellaneous group: This group includes electrorefining of common metals like copper, lead, tin, and so on using aqueous electrolytes and of
reactive metals like aluminum, magnesium, zirconium, and so on using fused salt electrolytes, and electrotransport method for ultra-purification.
Schematic flowsheet for producing PGMs. Production of high-density
concentrate at the top of the flowsheet is notable. The density concentrate joins
the electrorefining slimes, thereby bypassing flotation, smelting, converting and
electrorefining.
Schematic counter current leach process
 Methods for treating dilute and concentrated solutions (leach liquors)

✓ Enrichment – removing the metal values selectively from the leach solution and concentrating them while leaving
behind the impurities. (e.g. recovery of uranium by Ion Exchange or Solvent Extraction or recovery of gold on
Activated Carbon)
✓ Purification – removing the impurities from the leach solution leaving behind the purified metal values in solution
(e.g. removal of arsenic from copper sulfate, crystallization of specific salts from concentrated solutions,
cementation of cadmium from zinc solutions or iron as jarosite from zinc sulfate solutions).
 Solution Purification ✓ Solvent extraction (SX) purifies and upgrades the pregnant leach solution (PLS) produced by the
leaching operation to generate an electrolyte from which high quality copper cathode can be
• Precipitation electrowon.
• Cementation ✓ Most leach liquors, irrespective of the leaching process by which they are produced, are too dilute in
• Crystallization copper (1-10 g/L Cu), too impure (containing 1-20 g/L Fe, as well as other deleterious species), and
not sufficiently conductive for direct electrodeposition of high purity cathode copper. Electrolysis of
these solutions would produce soft, powdery, and impure copper deposits.
Selective Enrichment and Concentration ✓ Industrial electrowinning (EW) requires pure copper-rich electrolytes (45-55 g/L Cu) with high
• Activated Carbon conductivity. This high concentration of copper ensures that (a) Cu2+ ions are always available for
• Ion Exchange plating at the cathode surface at current densities that allow economical rates of plating, being readily
renewed by mass transfer, and (b) gives smooth, dense, high purity, readily marketable cathode copper.
• Solvent Extraction High conductivity of the electrolyte is provided by a high acid concentration, typically 175-190 g/L
• Iron hydroxides are very difficult to H2SO4.
✓ SX provides means for producing pure, concentrated Cu electrolytes from dilute, impure leach liquors.
filter.
• There is no production of Solvent Extraction/Ion Exchange
hydrometallurgical iron. ✓ Exchange of an ion on a solid or dissolved in an organic liquid with an ion dissolved in a
• Jarosite process to control and solution. Solvent extraction is liquid Ion exchange.
precipitate iron. Leach solution is mixed with an immiscible organic solvent.
• Liquid Solid Separations are a Key • Metal is transferred to the organic phase.
• Phase separate due to density differences.
for Hydrometallurgy !!!
• Organic phase is then stripped into aqueous phase to purify and concentrate it.
• 3 Fe2(SO4)3 + 2(NH4,Na)OH + 10 • Stripped organic phase is then recycled back to extract more metal.
H2O = 2(NH4,Na)Fe3(SO4)(OH)6 + 5 Solvent extraction is a continuous process. It operates on relatively clear and
H2SO4 concentrated solutions.
✓ Used extensively for recovering copper; ~ 30% of the world’s copper is producing using SX.
✓ Selective recovery of metal from other metals (even of the same type charge, Cu+2 from Fe+3).
✓ Load Cu+2 into an organic phase, reject all other metals. Strip Cu+2 into a purified solution.
 Solvent Extraction Reactions
Solvation; Exchange; Chelation
An extractant should fulfill the following process requirements :
(a) Efficiently extract Cu from the PLS at typical pH values of leach liquors;
(b) Efficiently strip Cu into the EWelectrolyte under the acid concentrations required
for typical electrolytes;
(c) Have economically rapid extraction and strip kinetics;
(d) Allow rapid and complete disengagement of the aqueous and organic phases in
both the extraction and strip circuits, i.e., not form a stable emulsion;
(e) Be insoluble in the aqueous phases;
(f) Be stable under extraction and strip conditions so that it can be recycled many
times;
(g) Not absorb sulfuric acid;
(h) Extract Cu preferentially over other metals in the PLS, particularly Fe and Mn
(which are detrimental to the subsequent EW step);
(i) Not transfer deleterious species from PLS to electrolyte, particularly Cl (which
causes pitting of copper cathodes in EW);
(j) Be soluble in an inexpensive petroleum distillate diluent;
(k) Be non-flammable, non-toxic, and non-carcinogenic.
Cementation
HYDROLYTIC PRECIPITATION
Precipitation and Reduction
Selective recovery of the dissolved metal values from solution.
Ion Exchange reactions involve the interchange of ions between an aqueous solution and insoluble solid resin.
• A two stage process;
– Adsorption: utilization of an anionic or cationic organic resin to remove metal ions from aqueous solution with a bed of
resin.
– Elution: recovery of metal ions in concentrated and purified form by passing small amount of eluent through loaded bed.
✓ Ion Exchange finds use in uranium and separation in nickel cobalt processing, precious metals or lanthanide processing.
✓ It is relatively expensive and usually operated batch wise or semi continuously.
✓ Can be used in turbid solutions. The first applications for ion exchange was in water softening using natural and
synthetic silicates. Uranium was the first metal to be recovered by IX on a large scale.
Activated Carbon
• Gold cyanide adsorption
• Adsorption: The accumulation of gases, liquids, or solutes on the surface of a solid or liquid.
• Absorption; occurs into the solid or liquid.
Adsorption on Activated Carbon
Porous, High SSA
• Done in columns (CIC) or agitated tanks (CIP or CIL).
• Two steps:
– Loading of the desired metal.
– Unloading the desired metal.
– Water washing used in between to remove entrained solution.

• Activated carbon is used primarily for concentrating gold

and silver from cyanide solution. Also used in molybdenum
processing and organic clean up.
• It is cheap but relatively slow for treating dilute solutions.
• It can be used in turbid solutions.
• For solution purification and upgrading, the adsorption
process with activated charcoal is an anionic Ion Exchange
phenomenon.
Comparison between different concentration-purification processes
Deciding Factors
❖ Electrorefining is used when an anode is cast from impure metal.
❖ Electrowinning is employed when the metal is already dissolved into
solution, or when it is more feasible to employ a hydrometallurgical
digestion step as opposed to casting impure anodes.
• Electrowinning is the electrodeposition of metals that have been placed in a solution via leaching.
• It is also named electroextraction.
• Process: an electrical current passes from an inert anode (it is where the oxidation occurs) through a leach solution
consisting of dissolved metal ions.
• Then the metal is recovered as it is deposited in an electroplating process onto the cathode where the reduction occurs. The
metal that results from the process is known as an electrowon.

• Electrowinning principle: any impure material can be leached into a conducting solution, then the DC voltage is applied
through the solution and the desired material can be extracted

❑ Limitations: metal concentration, temperature, acidity levels, chemical components etc.

• Electrowinning can be used as a processing step for the recycling of non-ferrous metals.
• Non-ferrous metals can be recycled infinitely without losing any of their properties.
• Electrowinning an ideal process to recover pure metals from complex, mixed metal feeds. Electrowinning can also be done
on a smaller scale. The most commonly electrowon metals are copper, gold, silver, zinc, cobalt, and nickel.
Stainless steel cathode blank (a) before and (b) after plating and (c)
copper starter sheet. Note the hanger tabs on the starter sheet and the
edge strips on the permanent cathodes. (d) Copper cathode sheets are
stripped from the blank by an automatic stripping machine, (e)
corrugated and packed, and (f) strapped for shipping. The corrugations
are introduced so that the cathode stack melts more easily when the
cathodes are melted and cast.
 Acid Mist Suppression Power requirement P=V×I
The oxygen bubbles that are produced at the anodes rise to the top of
the electrolyte where they burst into the atmosphere, carrying tiny rate of plating of Cu from solution is given by Faraday's Law
droplets of sulfuric acid with them>>>> can create a corrosive,
unpleasant, and unhealthy environment in the tankhouse.
m=MItξ/nF
where m is the mass of Cu plated (g); M is the molar mass of Cu (63.55 g/mol); I is the current
Solution
passed (A); t is the time for which the current is passed (s); ξ is the current efficiency (i.e., the
• Good ventilation is essential.
fraction of the total current used in producing Cu, n is the number of electrons involved in the
• large blowers or extraction fans on the sides of the tankhouse
• hoods over the cells. The acid mist is captured and sent to a plating of Cu; and F is the Faraday constant (96 485 C/mol of charge = 96 485 A/mol).
scrubber, while evaporation of the electrolyte is also reduced The theoretical energy consumption for plating one tonne of copper is
• Hollow polyethylene balls (~2 cm diameter) or Polypropylene beads P = (1.23 − 0.34) V × 2/mol × 96,485 A/(63.54 g/mol) = 2703 W/g =
(3 mm diameter) are usually floated, 5–10 cm deep, on the 754 kWh/t Cu
electrolyte.
• chemical mist suppression agents, such as a foaming agent or The ratio of the actual mass of Cu plated, compared to this theoretical
fluorocarbon surfactant, that modify the characteristics of the value, is defined as the current efficiency,
bursting bubbles, reducing their energy on their release at the ξ(%)=100 (measured mass of Cu plated/theoretical mass of Cu
surface of the electrolyte plated)
Current efficiencies in modern Cu EW plants range from 85–95%
Electrolyte Additives
• Cu EW plants dissolve smoothing agents in their electrolytes to
promote the plating of dense, smooth copper deposits with minimum
entrapment of electrolyte impurity.
• Guar gum (150–400 g per tonne of cathode) and modified starches
(polysaccharides) and polyacrylamides are widely used.
• Smoothing agents originating from natural products tend to break
down above current densities of about 300 A/m2 Morphology of copper cathode plated in the (a) absence and (b) presence of guar.
Electrorefining
Electrorefining entails electrochemically dissolving copper from impure copper
anodes (oxidation) into an electrolyte containing CuSO4 and H2SO4 and then
electrochemically depositing pure copper from the electrolyte onto stainless steel or
copper cathodes. The process is continuous.

• Cu2+ cations in electrolyte migrate to the cathode by convection and diffusion

• The electrons and Cu2+ ions recombine at the cathode surface to form copper metal

• Resistance to current flow must be overcome by applying a potential between the

anode and cathode.
• Small overvoltages must also be applied to plate copper on the cathode (~0.05 V) and
dissolve copper from the anode (~0.1 V). Ohmic drops across the electrolyte and
electrical contacts. Applied industrial anode–cathode potentials are ~0.3 V.
• Insoluble impurities in the anode adhere to the anode or fall to the bottom of the
refining cell and often consist of valuable rare elements, including gold, silver, and
selenium. They are removed and sent to a Cu and byproduct metal recovery plant.
• Soluble impurities leave the cell in continuously flowing electrolyte. They are
removed from an electrolyte bleed stream.
• The electrorefining process allows to separate heavy metals, including plutonium,
caesium, and strontium, from the less-toxic bulk of uranium.
 • Industrial electrorefining uses large
(~1 m × 1 m), thin (40–50 mm)
copper anodes and thin (1–10 mm)
cathodes interleaved approximately
50 mm apart in a cell filled with
electrolyte.
• The anodes in the cell are all at the
same potential: the cathodes are
all at another, lower potential.
• DC Power is provided by a rectifier.
• Anodes and cathodes are evenly
spaced along the cell to ensure an
even distribution of current to all
electrodes.

Electrorefined copper
Copper anodes with a typical purity of 98.5–99.5% Cu are electrorefined to produce cathodes with a cathodes plated onto
purity of >99.997% Cu. Electrorefined copper, melted and cast, contains less than 20 parts per stainless steel blanks

million (ppm) impurities, plus oxygen which is controlled at 0.018–0.025%

Chemistry of Electro-refining and Behavior of Anode Impurities
• The principal impurities in copper anodes are Ag, As, Au, Bi, Co, Fe, Ni, O, Pb, S,
Sb, Se, and Te
• They must be prevented from entering the cathode copper.
• behavior is governed by their position in the electrochemical series
• At the anode, elements with less positive reduction potentials than Cu dissolve under
the applied potential, while elements with more positive reduction potentials remain
in solid form.
• At cathode, elements with more positive reduction potentials deposit preferentially,
while elements with more negative potentials remain in solution.
The quantity of metal deposited from an electrolyte is in accordance with the
Faraday laws:
(1) quantity is proportional to the number of ampere-hours
(2) a given number of ampere-hours will deposit an equivalent amount of any metal,
the equivalent being determined by dividing the atomic weight by the valence
The power requirement (W) for electrolytic production of metals is determined,
basically, by the ampere- hour (I) requirement, combined with the cell-voltage (V).
W=VI; Watts = Volts x Amperes
As metal is deposited by direct current, the power requirement of an electrolytic plant
include line-rectifier/transformer losses
 Titanium Production process
Ilmenite/anatase Ore: TiO2

CaCl2+CaO

Kroll process for Ti production FFC Cambridge process for Ti production

For in-depth study: Fray, D. J. (2008). Novel methods for the production of titanium. International Materials Reviews, 53(6), 317-325.
Gold Production process

Iin-depth study: noue, K., Parajuli, D., Gurung, M., Pangeni, B., Khunathai, K., Ohto, K., & Kawakita, H.
(2019). Gold Recovery Process from Primary and Secondary Resources Using Bioadsorbents. In Elements
of Bioeconomy. IntechOpen.
Platinum Production process

In-depth study: Thethwayo, B. M. (2018). The extraction of platinum group metals. Noble and precious metals-Properties, nanoscale effects and applications, 302-403.
Tin production process Smelting process of tin concentrate
Mineral concentration of tin ore (~60% Sn)

Primary ore (<1% Sn)

(20-30% Sn)

(99.9% Sn)

For in-depth study: (1) Angadi, S. I., Sreenivas, T., Jeon, H. S., Baek, S. H., & Mishra, B. K. (2015). A review of cassiterite
Simplified process of Tin extraction beneficiation fundamentals and plant practices. Minerals Engineering, 70, 178-200; (2) http://www.madehow.com/Volume-
4/Tin.html.
 For open pit and

Uranium Production process underground mining

For in-depth study: (1) https://www.nrc.gov/materials/uranium-recovery/extraction-methods/isl-recovery-facilities.html (2)

http://large.stanford.edu/courses/2012/ph241/weil2/
Nickel Production process
Primary Ore: Lateritic (Garnierite; (Ni, Mg)8Si4O10(OH)8)), Sulphide (Pentlanide; (FeNi)9S8)

For sulphide ore

Carbonyl process
Zirconium Production process

Electro refining process for Zr production Kroll process for Zr production

In-depth study: Takeda O, Uda T, Okabe TH (2014) 2. Non-ferrous process principles and production technologies, Chapter 2.2 rare earth, titanium group metals, and reactive metal production.
In: Seetharaman S (ed) Treatise on process metallurgy, vol 3. Elsevier Inc, Oxford, pp 995–1069
Beryllium Production process
Beryl Ore: 3BeO·Al2O3·6SiO2 (~11% BeO)

Fluoride process
Reactions involved in the fluoride process:

Kroll process
In-depth study: (1) Thorat, D. D., Tripathi, B. M., & Sathiyamoorthy, D. (2011). Extraction of beryllium from Indian beryl by ammonium hydrofluoride. Hydrometallurgy, 109(1-2), 18-22. (2)
Morana, S. J., & Simons, G. F. (1962). Beryllium extracted by the fluoride process. JOM, 14(8), 571-574.
Thorium Production process
Acid cracking process

Alkaline leaching process

In depth study: Salehuddin, A. H. J. M., Ismail, A. F., Bahri, C. N. A. C.

Z., & Aziman, E. S. (2019). Economic analysis of thorium extraction
from monazite. Nuclear Engineering and Technology, 51(2), 631-640.