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A short history of hydrometallurgy

Article in Hydrometallurgy · September 2005

DOI: 10.1016/j.hydromet.2004.01.008

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 Hydrometallurgy 79 (2005) 15 – 22
www.elsevier.com/locate/hydromet

A short history of hydrometallurgy

Fathi Habashi
Department of Mining, Metallurgical, and Materials Engineering, Laval University, Quebec City, Canada G1K 7P4
Received 9 January 2003; received in revised form 19 December 2003; accepted 29 January 2004
Available online 28 July 2005
Dedicated to the memory of Vladimir N. Mackiw (1923–2001), a distinguished Canadian hydrometallurgist

Abstract

Thousands of years ago people had learned how to build furnaces and use fire to melt rocks and produce metals but the use
of aqueous solutions for ore processing came much later, mainly at the time of the alchemists when acids and alkalies became
known and used. Modern hydrometallurgy, however, can be traced back to the end of the 19th century when two major
operations were discovered: the cyanidation process for gold and silver extraction and the Bayer process for bauxite treatment.
Later, in the 1940s, a breakthrough came during the Manhattan Project in USA in connection with uranium extraction. Since
then, it has been advancing progressively and even replacing some pyrometallurgical processes. Canadian contribution is
significant particularly in the recovery of uranium, nickel, cobalt, and zinc.
D 2005 Elsevier B.V. All rights reserved.

1. Introduction time that blue vitriol contained copper. The major

question, however, that remained unanswered was:
The roots of hydrometallurgy may be traced back how can the transmutation of iron or copper into
to the period of alchemists when the transmutation of gold be effected? Gold, the most noble of all metals
base metals into gold was their prime occupation dissolved in mercury forming an amalgam but was
(Habashi, 1993a). Some of these operations involved insoluble in all acids or alkalies known at that time.
wet, i.e., hydrometallurgical methods. For example, The discovery of aqua regia by Jabir Ibn Hayyan
when an alchemist dipped a piece of iron into a (720–813 AD) (Fig. 1), the Arab alchemist, may be
solution of blue vitriol, i.e., copper sulfate, the iron considered as a milestone marking the beginning of
was immediately covered by a layer of metallic cop- hydrometallurgy. Aqua regia, i.e., royal water, is a
per. This apparent transmutation of iron into copper is mixture of HCl and HNO3 that dissolves gold; neither
represented in modern terms by the equation: of the acids alone has any dissolving action. Aqua
Cu2+ + FeYCu + Fe2+, but it was not known at that regia is still used today for gold refining, and chlorine
one of its active ingredients: 3HCl + HNO3 Y Cl2 +
NOCl + 2H2O was utilized extensively for extracting
E-mail address: fathi.habashi@gmn.ulaval.ca. gold from its ores till the 1890s.
0304-386X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2004.01.008
16 F. Habashi / Hydrometallurgy 79 (2005) 15–22

lime kilns, then agitated with water, filtered, then

evaporated to dryness to yield potash. One ton potash
required the burning of 400 tons of hardwood, which
is equivalent to the cutting of about 10 acres of forest.

2. The beginnings

The birth of modern hydrometallurgy dates back to

1887 when two important processes were invented.
Fig. 1. The Arab alchemist Jabir Ibn Hayyan (720–813 AD), dis-
The first, the cyanidation process for treating gold
coverer of aqua regia (royal water) for dissolving gold—the king of ores, and the second, the Bayer Process for the pro-
metals. duction of alumina.

In the Middle Ages, certain soils containing putre- 2.1. Cyanidation process
fied organic matter were leached to extract saltpeter
(= salt of stone, potassium nitrate), a necessary ingre- The dissolving action of cyanide solution on metal-
dient for the manufacture of gunpowder. The process lic gold was known as early as 1783 by the Swedish
was fully described by Vannoccio Biringuccio (1480– chemist Carl Wilhelm Scheele (Habashi, 1987). L.
1539) in his Pirotechnia published in 1540. Elsner in Germany in 1846 studied this reaction and
In the 16th century, the extraction of copper by wet noted that atmospheric oxygen played an important
methods received some attention. Heap leaching was role during dissolution. The application of this knowl-
practiced in the Harz mountains area in Germany and in edge to extract gold from its ores was proposed and
Rı́o Tinto mines in Spain. In these operations, pyrite patented much later in England by John Stewart
containing some copper sulfide minerals was piled in MacArthur (1856–1920) (Fig. 2) in 1887 and became
the open air and left for months to the action of rain and known as the cyanidation process. G. Bodländer in
air whereby oxidation and dissolution of copper took 1896 made the important discovery that hydrogen
place. A solution containing copper sulfate was drained peroxide was formed as an intermediate product dur-
from the heap and collected in a basin. Metallic copper ing the dissolution of gold.
was then precipitated from this solution by scrap iron, a
process that became known as bcementation processQ,
which is apparently derived from the Spanish
bcementaciónQ meaning precipitation. This is the
same process that was already known to the alchemists
and is still in operation today to an appreciable extent.
In the 18th century, one of the most important
industries in Quebec was the production of potash
for export to France to satisfy the needs of the soap
and glass industries. Before the invention of the
Leblanc Process for the manufacture of Na2CO3
from NaCl, the main source of Na2CO3 was from
ashes of seashore vegetation, and that of potash was
from ashes produced by burning wood in areas where
the clearing of forests was in progress on a large scale.
The importance of this process to hydrometallurgy
lies in the fact that leaching was extensively practiced.
During the period 1767–1867, wood ash was col- Fig. 2. John Stewart MacArthur (1856–1920), discoverer of the
lected from domestic stoves and fireplaces, and from cyanidation process.
 F. Habashi / Hydrometallurgy 79 (2005) 15–22 17

The cyanidation process had already been applied to

each mining district in the world and still its chemistry
was very obscure. Its impact on hydrometallurgy had
been tremendous. Extremely large reactors known as
Dorr agitators in which the finely ground ore was
agitated with the cyanide leaching agent and equipped
with compressed air injection in the pulp had been
designed and built by the metallurgical engineer John
Dorr. Huge filtration plants designed to obtain clear
leach solutions for metal recovery were similarly con-
structed. The ancient process known as cementation
which was applied only for precipitating copper from
solution by scrap iron was applied to gold solutions,
iron being replaced by zinc. In spite of all these
advances in engineering and the wide application of Fig. 4. Karl Josef Bayer (1847–1904), inventor of the process for
the production of alumina from bauxite.
the process, the theory still remained lagging behind.
As a result of introducing the cyanidation process pure Al2O3 and known as the Bayer Process (Haba-
worldwide, gold production increased greatly during shi, 1995). This process was concerned with leaching
the period 1900–1910 (Fig. 3). bauxite, discovered in 1821 in France in a small
village called Les Baux, near Marseille, with sodium
2.2. Bayer process hydroxide solution above its boiling point in a pres-
sure reactor. After separating the insoluble material,
The second major hydrometallurgical process of the pure solution was then seeded to precipitate pure
this era was the process invented by Karl Josef crystalline aluminum hydroxide which was filtered,
Bayer (1847–1904) (Fig. 4) for the preparation of washed, dried, and calcined to pure Al2O3 suitable for
charging to the electrolytic reduction cell invented 2
years earlier. Bayer was an Austrian chemist working
in Saint Petersburg, in Russia; his process is used at
present in its original version with practically no
change. It is interesting to point out the following:

! The process was originally developed to satisfy the

needs of the textile industry since aluminum hydro-
xide was used as a mordant in dyeing cotton. It was
only after the invention of the electrolytic alumi-
num process in 1886 that the process gained impor-
tance in metallurgy.
! Bayer’s first contribution was in 1887 when he
discovered that Al(OH)3 precipitated from alkaline
solution was crystalline, easy to filter, and wash
free from impurities while that precipitated from
acid medium by neutralization was gelatinous and
difficult to filter and wash.
! A few years earlier to Bayer’s invention, Louis Le
Chatelier (1815–1873) in France described a
method for making Al2O3 by heating bauxite
Fig. 3. Increase in world gold and silver production between 1900 with Na2CO3 at 1200 8C, leaching the sodium
and 1910 as a result of introducing the cyanidation process. aluminate formed with water, then precipitating
18 F. Habashi / Hydrometallurgy 79 (2005) 15–22

Na2CO3 Na2CO3
bauxite bauxite

NaOH
SINTERING SINTERING bauxite

water water
PRESSURE
LEACHING LEACHING LEACHING

FILTRATION residue FILTRATION residue FILTRATION residue

seed seed
CO2

PRECIPITATION PRECIPITATION PRECIPITATION

FILTRATION FILTRATION FILTRATION

solution solution solution

EVAPORATION EVAPORATION EVAPORATION

TO DRYNESS TO DRYNESS

AI (OH)3 AI (OH)3 AI (OH)3

LE CHATELIER BAYER BAYER

1855 1888 1892
Fig. 5. Bayer process displaced Le Chatelier pyrometallurgical route.

Al(OH)3 by CO2 which was then filtered, dried, from the sodium nitrate deposits in Chile by treat-
and claimed to pure Al2O3. This process was ment with concentrated H2SO4. It became relatively
abandoned in favor of the Bayer process (Fig. 5). cheap only after the invention of Haber’s process
since nitric acid is made now exclusively by the
oxidation of ammonia.
3. Further development Towards the beginning of the 20th century, hydro-
metallurgy of copper received a particular attention.
At the beginning of the 20th century numerous Oxide ores were leached on large scale by dilute
leaching and recovery processes were proposed, sulfuric acid in Chile. Copper sulfides were also
some of them were put into practice, others had to solubilized due to the presence of ferric ion which
wait for about half a century until they were applied, acted as an oxidizing agent. Instead of precipitating
while others never developed beyond a pilot plant. copper from leach solution by scrap iron in the usual
When examining the patent literature at the begin- way, electrowinning was used in Chile in 1912 (Haba-
ning of this century it is remarkable to see the large shi, 1998). The First World War (1914–1918) created
variety of leaching agents proposed. In 1903, M. a demand for the zinc for the manufacture of cartridge
Malzac in France proposed the use of ammonia brass. Zinc for this purpose used to be obtained by the
solutions for leaching sulfides of copper, nickel, distillation of commercially available metal in Bel-
and cobalt. At that time NH3 was an expensive gium and Germany from ore supplied by Australia.
reagent obtained exclusively as a by-product of the This situation inspired industry in North America to
coal industry. It became a cheap commercial reagent supply additional metal from ores that were not amen-
only after its synthesis 10 years later by Fritz Haber able to standard methods. At Trail in British Columbia
in Germany. Nitric acid was proposed by Kingsley in and Anaconda in Montana, the processes for electro-
1909 for leaching sulfide ores. Also, at that time lytic zinc and the leaching of a large tonnage of ZnO
HNO3 was an expensive reagent obtained exclusively by H2SO4 was introduced. The process is mainly
 F. Habashi / Hydrometallurgy 79 (2005) 15–22 19

based on a patent by L. Létrange in France issued in ments some Canadian coins were produced for over
1881 (Ingallis, 1936). Cadmium gradually emerged as 40 years using hydrometallurgical technique. Also,
an important by-product of this process. during this period, the recovery of uranium as a by-
product of phosphate fertilizers was achieved by its
extraction from phosphoric acid by organic solvents.
4. Development during World War II Although this process was abandoned a few years
later when important uranium deposits were discov-
In the 1940s, the technology of uranium production ered, now it has been revived in view of the expansion
was introduced in connection with the Manhattan in nuclear energy programs.
Project—a US project aimed at producing an atomic In the late 1950s INCO built a semi-commercial
bomb. Numerous new techniques became suddenly plant for treating its low-grade pentlandite–pyrrhotite
used on large scale. Some of these are, for example, concentrate based on oxidation to eliminate the sulfur
the use of Na2CO3 as a leaching agent, ion exchange, content as SO2, controlled reduction of the oxides to
solvent extraction, and many processes for precipita- form metallic nickel which was leached by ammonia
tion from aqueous solutions. A large number of syn- (Fig. 7). The plant, however, was shut down a few
thetic resins for use as ion exchangers and, similarly, a years later, being uneconomical besides the pollution
large number of organic solvents were specially problems associated with the large tonnage of SO2
synthesized for use as extractants for uranium. Separa- emitted in the atmosphere. During the same period the
tion of the rare earths by ion exchange replaced the mechanism of dissolution of sulfides was well estab-
tedious fractional crystallization from solution. Later lished and the formation of elemental sulfur during
on, solvent extraction replaced ion exchange and an the aqueous oxidation of sulfides became well known
industrial plant went into operation at Mountain Pass (Fig. 8). Work at the Mines Branch in Ottawa (known
in USA producing high purity rare earths using about today as CANMET) demonstrated that pyrrhotite–
1000 mixer-settlers (Habashi, 1993b). penthandite concentrate could be treated in autoclaves
at 120 8C under oxygen pressure to get nickel in
solution while Fe2O3 and elemental sulfur remain in
5. Recent advances the residue (Fig. 9). The process was later applied by
the Russians at the Norilsk plant for nickel recovery
In the 1950s, pressure hydrometallurgy was intro- but unfortunately not by INCO to replace their ammo-
duced for leaching sulfide concentrates (Sherritt-Gor- nia process mentioned above.
don process), for laterites (Moa process) (Fig. 6), for In the 1960s, the role of bacteria in leaching
tungsten ores, as well as for the direct precipitation of became known and the widespread use of heap and
metals from solution. As a result of these develop- in situ leaching for extracting copper was practiced.

Fig. 6. Laterite pressure leaching plant in Cuba.

20 F. Habashi / Hydrometallurgy 79 (2005) 15–22

Pyrrhotitic Make up
nickel ore H2SO4
Sulfide
SO2 concentrate
Roasting O2

Leaching
Reduction
NH4OH + (NH4)2CO3 Filtration
Air Gangue, S, PbSO4
FeOOH
Leaching
Purification

Filtration
Spent Electrolysis
electrolyte
Drying Purification
Metal

Sintering Filtration Fig. 9. Flow sheet showing the formation of elemental sulfur during
the aqueous oxidation of sulfide concentrates.

Fe2O3 Boiling Absorption Energy Commission, the application of organic sol-

vents, mainly oximes, for extracting copper from
Filtration
solution was realized. At present, about 20% of the
copper is now produced by hydrometallurgical tech-
Basic nickel carbonate nique (Habashi, 1999).
Calcination
In the 1970s the pressure leaching of zinc sulfide
concentrates was applied industrially in Canada. The
NiO new process, which is essentially the same as that
Fig. 7. Flow sheet of INCO ammonia leaching process that was shut shown in Fig. 9, rendered the production of zinc a
down because of economic considerations and SO2 emissions. fully hydrometallurgical process, thus displacing the
horizontal retort process based on roasting ZnS,
The same technique was later adopted for leaching reduction of ZnO by carbon, and distillation refining
low-grade uranium and gold ores. In the same period, of metallic zinc developed in 1740 even after a num-
as a result of de-classifying reports by the US Atomic ber of modifications (Fig. 10). The process has also
the advantage of liberating the zinc industry from the
necessity of producing sulfuric acid. In the 1980s, the
hydrometallurgy of gold dominated the scene: wide-
spread application of activated charcoal for gold

ZnS
SO2
Air Roasting Acid Plant H2SO4
C ZnO
Reduction
Gases
Condenser CO, CO2
Raw Zn
Distillation Cadmium

Pure Zinc

Fig. 10. The pyrometallurgical process for zinc production was

Fig. 8. Regions of stability of elemental sulfur at 100 8C. replaced by the hydrometallurgical route shown in Fig. 9.
 F. Habashi / Hydrometallurgy 79 (2005) 15–22 21

Table 1 Table 1 (continued)

Summary of historical development in hydrometallurgy Recent advances
Early period 1960s Discovery of the role played by microorganisms
7th century The apparent transmutation of iron into copper in leaching processes and the widespread use of
by alchemists (Cu2+ + FeYCu + Fe2+) heap and in situ leaching for extracting copper
8th century The discovery of aqua regia by the Arab alchemist from low-grade material. The application of
Jabir Ibn Hayyan (720–813 AD). This was the pressure leaching to a variety of raw materials,
only known solvent for gold. Still used today in e.g., laterites, tungsten ores, uranium ores. The
gold refining. application of solvent extraction for copper.
16th century Heap leaching of copper-containing pyrite in the 1970s Discovery of galvanic action in leaching sulfide
Harz mountains in Germany and in Rı́o Tinto in minerals. Recovery of traces of uranium from
Spain, and the precipitation of copper from the waste leach solutions after copper precipitation
solutions by iron. with scrap iron. Pressure leaching of zinc sulfide
18th century Production of potash for soap and glass industries concentrate in dilute H2SO4 at Trail and Timmins
by leaching ashes left after burning wood, e.g., in in Canada.
Quebec, where the clearing of forests was in 1980s The hydrometallurgy of gold greatly advanced:
progress on large scale. widespread application of activated carbon
technology, and aqueous oxidation of gold
Modern era refractory ores.
1887 The invention of the cyanidation process, i.e.,
dissolution of gold from ores by a dilute sodium
cyanide solution and the precipitation of gold from
the solutions by zinc. The invention of Bayer’s
process: precipitation of crystalline Al(OH)3 from adsorption and the aqueous oxidation of gold refrac-
sodium aluminate solution by seeding, followed in tory ores were industrialized. Large autoclaves are
1892 by his invention of pressure leaching of now used for this purpose.
bauxite by NaOH solution.
1912 Recovery of copper from leach solution in Chile
by electrolysis.
1916 The use of ammonium hydroxide for leaching 6. Epilogue
native copper ore in Lake Superior District, and
for malachite-azurite ore in Alaska. Development Hydrometallurgy is vigorously competing with old
of the hydrometallurgical electrowinning zinc pyrometallurgical techniques, and in some cases it has
process at Trail and Anaconda. The recovery
displaced such processes. For example:
of cadmium as a by-product of the zinc
hydrometallurgical process.
1924 Caron process for ammonia leaching of metallic ! The sodium carbonate sintering process for treating
nickel produced by reduction of laterites. bauxite developed in 1855 was displaced by the
1927 Henglein process for pressure leaching of ZnS at pressure leaching process in 1892.
high temperature in the presence of oxygen.
! The pyrometallurgical route for zinc was displaced
1930 Sullivan process for ambient leaching of copper
sulfides by ferric chloride solution. in 1970s by pressure leaching of ZnS followed by
electrowinning of zinc from the purified zinc sul-
Development during World War II fate solution.
1940s Development of the uranium technology in ! There is a good opportunity that nickel sulfides
connection with the US Manhattan Project aimed
could be treated by hydrometallurgical route simi-
at producing an atomic bomb. Introduction of
sodium carbonate as a leaching agent for uranium, lar to the ZnS process—elemental sulfur being
the widespread use of ion exchange and solvent obtained instead of SO2.
extraction for uranium recovery, and the separation ! The treatment of chalcopyrite concentrate by pres-
of the lanthanides by ion exchange. sure leaching has been recently piloted by Phelps
Dodge in Arizona as a new method competing with
Recent advances
1950s The application of pressure hydrometallurgy for smelting.
leaching nickel sulfide ores and the precipitation
of pure nickel from solution by hydrogen under Table 1 gives a summary of the historical develop-
pressure. ment in hydrometallurgy.
22 F. Habashi / Hydrometallurgy 79 (2005) 15–22

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