1

TECNOLÓGICO NACIONAL DE MÉXICO

INSTITUTO TECNOLÓGICO DE LA LAGUNA

TEMA I

ACTIVIDAD 2: TRABAJO DE INVESTIGACIÓN (RESUMEN DE

ARTÍCULOS CIENTÍFICOS)

HIDROMETALURGIA

GPO: 25JA

DOCENTE: PEDROZA FIGUEROA SIMÓN ALBERTO

EQUIPO NO. 5

MUÑOZ ARELLANO DIEGO 19131578

PALACIOS BANDA ANDREA ELITH 19131382
REYNA CHÁVEZ ADRIÁN GUILLERMO 19130475
RÍOS SILVA JAVIER 19130477
VALDÉS GONZÁLEZ RAFAEL 19130500

TORREÓN, COAH. 07/02/2023

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Article I: A short history of hydrometallurgy by Fathi Habashi

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. The hydrometallurgy has be traced back to the period when the alchemists tried to
make base metals into gold, some of these operations involved in hydrometallurgical
methods and other ways for different metals.

The gold recovery was the first movement to start the investigation of metal extraction,
gold; the most noble of all metals dissolved in mercury forming an amalgam but was
insoluble in all acids or alkalies known at that time. The discovery of aqua regia by the
Arab alchemist Jabir Ibn Hayyan, may be considered as the beginning of hydrometallurgy.

However, what is the aqua regia? Aqua regia or royal water is a highly oxidizing mixture
of HCl and HNO3 that dissolves gold; neither of the acids alone has any dissolving action.
Aqua regia is still used today for gold refining, and chlorine, it was utilized extensively for
extracting gold from its ores until the 1890s.

Certain events marked the history of hydrometallurgy, some of these are:

In the middle ages, certain soils containing putrefied organic matter were leached to
extract saltpeter (salt of stone, potassium nitrate) a necessary ingredient for the
manufacture of gunpowder.

In the 16th century, the extraction of cooper by wet methods, as heap leaching was
practiced in the Harz Mountain in Germany and in Río Tinto mines in Spain. In these
operations, pyrite containing some copper sulfide minerals was piled in the open air and
left for months to the action of rain and air whereby oxidation and dissolution of copper
took place. A solution containing copper sulfate was drained from the heap and collected
in a basin. Metallic copper was then precipitated from this solution by scrap iron, a process
that became known as “cementation process”, which is apparently derived from the
Spanish “cementación” meaning precipitation. This is the same process that was already
known to the alchemists and is still in operation today to an appreciable extent.
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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.

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 birth of modern hydrometallurgy dates back to 1887 when two important processes
were invented: Cyanidation process and Bayer process.

The first process is the dissolving action of cyanide solution on metallic gold was known
as early as 1783 by the Swedish chemist Carl Wilhelm Scheele . L. Elsner in Germany,
in 1846 studied this reaction and noted that atmospheric oxygen played an important role
during dissolution. The application of this knowledge to extract gold from its ores and in
1896 made the important discovery that hydrogen peroxide was formed as an
intermediate product during the dissolution of gold. 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 constructed.

The second major hydrometallurgical process of this era was the process invented by
Karl Josef Bayer (1847–1904), this method called Bayer process discovered in 1821 in
France, for the preparation of pure Al2O3 was concerned with leaching bauxite, with
sodium hydroxide solution above its boiling point in a pressure reactor. After separating
the insoluble material, the pure solution was then seeded to precipitate pure crystalline
aluminum hydroxide which was filtered, washed, dried, and calcined to pure Al2O3 suitable
for charging to the electrolytic reduction cell invented 2 years earlier.
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At the beginning of the 20th century numerous leaching and recovery processes were
proposed, some of them were put into practice, others had to wait for about half a century
until they were applied, while others never developed beyond a pilot plant. In 1903, they
proposed the use of ammonia solutions for leaching sulfides of cooper, nickel and cobalt.
At that time NH3 was an expensive reagent obtained only as a by-product of the coal
industry, 10 years late it became a cheap commercial reagent. Then nitric acid was
proposed for leaching sulfide ores, and they had the same situation than the previous
acid, it could only be obtained from the sodium nitrate deposits in Chile by treatment with
concentrated H2SO4.

Towards the beginning of the 20th century, hydrometallurgy of copper had its
development, oxide ores were leached on large scale by dilute sulfuric acid. Copper
sulfides were also solubilized due to the presence of ferric ion which acted as an oxidizing
agent. Instead of precipitating copper from leach solution by scrap iron in the usual way,
electrowinning.
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The First World War (1914–1918) created a demand for the zinc for the manufacture of
cartridge brass Zinc for this purpose used to be obtained by the distillation of commercially
available metal. The processes for electrolytic zinc and the leaching of a large tonnage of
ZnO by H2SO4 was introduced. The process is mainly based on a patent by L. Le´trange
in France issued in 1881, Cadmium gradually emerged as an important by-product of this
process.
The development during the world war II, in the 1940’s , the technology of uranium
production was introduced in connection with the Manhattan Project aimed at producing
an atomic bomb, numerous new techniques became suddenly used on large scale. Some
of these are, for example, the use of Na2CO3 as a leaching agent, ion exchange, solvent
extraction, and many processes for precipitation from aqueous solutions. A large number
of synthetic resins for use as ion exchangers and, similarly, a large number of organic
solvents were specially synthesized for use as extractants for uranium. Separation of the
rare earths by ion exchange replaced the tedious fractional crystallization from solution.
Later on, solvent extraction replaced ion exchange.

The recent advances in the late 1950s INCO built a semi-commercial plant for treating its
low-grade pentlandite–pyrrhotite concentrate based on oxidation to eliminate the sulfur
content as SO2, controlled reduction of the oxides to form metallic nickel, which was
leached by ammonia. During the same period, the mechanism of dissolution of sulfides
was well established and the formation of elemental sulfur during the aqueous oxidation
of sulfides became well known. Work at the Mines Branch in Ottawa demonstrated that
pyrrhotite– penthandite concentrate could be treated in autoclaves at 120 °C under
oxygen pressure to get nickel in solution while Fe2O3 and elemental sulfur remain in the
residue. The process was later applied by the Russians at the Norilsk plant for nickel
recovery but unfortunately not by INCO to replace their ammonia process mentioned
above.

In the 1960s, the role of bacteria in leaching became known and the widespread use of
heap and in situ leaching for extracting copper was practiced. The same technique was
later adopted for leaching low-grade uranium and gold ores and in the same period the
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US Atomic Energy Comission reports that about 20% of the copper is now produced by
hydrometallurgical technique.

Finally in the 70’s to 80’s the pressure leaching of zinc sulfide concentrates was applied
industrially rendered the production of zinc a fully hydrometallurgical process, thus
displacing the horizontal retort process based on roasting ZnS, reduction of ZnO by
carbon, and distillation refining of metallic zinc The process has also the advantage of
liberating the zinc industry from the necessity of producing sulfuric acid. The
hydrometallurgy of gold dominated the scene: widespread application of activated
charcoal for gold adsorption and the aqueous oxidation of gold refractory ores were
industrialized. Large autoclaves are now used for this purpose.

Nowadays, hydrometallurgy is vigorously competing with old pyrometallurgical

techniques, and in some cases it has displaced such processes.
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Article II: Hydrometallurgical process for extraction of metals from

electronic waste – part 1: material characterization and process option
selection by Zeljko Kamberovic.

Fast electronic industry development brought the great benefits in everyday life, but its
consequences are usually ignored or even unknown. Used electronic equipment became
one of the fastest growing waste streams in the world. From 20 to 50 million Tonnes of
waste electrical and electronic equipment are generated each year, bringing significant
risks to human health and the environment. EU legislative restricts the use of hazardous
substances in electrical and electronic equipment.

Recycling of printed circuit boards, as a key component in the WEEE, in past two decades
have been based on recovery via material smelting. Goosey and Kellner in their detailed
study have defined the existing and potential technologies that might be used for the
recycling of PBCs. They potential out that metals could be recycled by mechanical
processing, pyrometallurgy, hydrometallurgy, Bio metallurgy or a combination of these
techniques.

Hydrometallurgy, I.e., leaching and cementation process in Serbian mine Bor was first
mentioned in 1907 when 200 tons of copper were produced. Hydrometallurgical
processing consists of leaching-transferring desirable components into solution using
acids or halides as leaching agents, purification of the leach solution to remove impurities
by solvent extraction, absorption or ion- exchange then recovery of base and precious
metals from the solution by electrorefining process, chemical reduction, or crystallization.
Oishi et al, conducted research on recovery of copper from PBCs by hydrometallurgical
techniques, proposed process consists of leaching, solvent extraction and electrowinning.
In the first stage of research conducted by Veit et al mechanical processing was used as
comminution followed by size, magnetic and electrostatic separation. After pretreatment,
the fraction with concentrated Cu, Pb and Sn was dissolved with acids and treated in an
electrochemical process in order to recover the metals separately, especially copper, with
two different solutions: aqua regia and sulphuric acid.
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Electronic waste is defined as a mixture of various metals, particularly copper aluminum

and steel, attached to different types of plastics and ceramics. The samples for
experimental research presented in this paper were milled PCBs with obtained by
mechanical pretreatment of waste computers. The first stage was manual disassembling
of computers, liberation of PCBs and removal of batteries and capacitors. Liberated PCBs
were milled in QZ-decomposer, separating magnetic materials from non-magnetic
fractions, while aluminum was manually removed from conveyor belt. Material was then
milled in shedder Meccano Plastica, after Wich material was not exposed to another
magnetic separation. Characterization of granulated waste PCBs included determination
of following parameters: pouring density, percentage of magnetic fraction, particle size
distribution, rate of metal components leachability using optical microscopy, atomic
absorption spectrometry (AAS), X-ray fluorescent spectrometry (XRF) and volumetric
analysis. Also, appropriate hydrometallurgical system for evaluation of metal components
and optimization of process parameter: temperature, time, solid:liquid ratio and mixing
velocity are selected.

Content of metallic and non-metallic components of entire sample as well as for each
fraction was determined by leaching with 50 vol% HNO3 near to boiling temperature with
agitation followed by filtration after cooling. Metallic fraction is transferred to liquid. Solid
non-metallic residue mass is measured after filtration.
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Result of the sieve analysis showed that the greatest percent of sample was in fraction
+2.5mm. Metallic part was mostly contained in fraction +0.8 mm

Analysis of chemical composition of granulated PCBs was performed using volumetric

analysis, AAS and XRF spectrometry. Materials used for presented analysis were both
granulated samples and samples after sieve analysis dissolved in 50 vol% HNO3

Volumetric analysis was performed using standard sodium thiosulphates solution for
treatment of samples dissolved in 50 vol% HNO3. Results showed that copper content in
granulated PCBs was 21.61 wt%. Also, distribution of copper in fractions was
determinated by volumetric analysis.

Presented results show that copper is mostly concentrated in fraction +0.8 mm. AAS was
used for analyzing solutions of each fraction, obtained by dissolving in 50 vol% HNO3, in
order to determine content of Cu, Zn, Fe, Ni, Pb. It was performed by Perkin Elmer 4000
spectometer calibrated with standard solutions for each measured metal.
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Fraction +5mm contained 6% of Fe. Wich means that magnetic separation was not
efficient enough for this size of particles. XRF spectrometry was used for direct analysis
of granulated PCBs samples. Characteristics parts like contacts, solders and composites
were analyzed XRF analysis was performed on Skyray EDX 3000.

XRF analysis showed that metal Contant varies from sample to sample and it highly
depends on measuring spot. Based on detailed literature review and presented
experimental results, several process options were selected as an appropriate
hydrometallurgical process for extraction of metals from electronic waste was.
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Article III: A Review of Niobium-Tantalum Separation in

Hydrometallurgy by Olushola S. Ayanda.

Niobium is a rare, soft, grey and ductile transition metal with the symbol Nb. It was
discovered by Charles Hatchett, an English chemist , in 1801 [Niobium is used in
superconducting magnets, commemorative coins, medical device, jewelries, arc-tube
seals, capacitors, optical lens, barometer, nuclear applications, superconducting RF
cavities, electromagnetic radiation detector and it is used in nickel-, cobalt-, and iron
based super-alloys which are used in jet engines components, rocket sub-assemblies,
heat resistant and combustion equipments.

Tantalum was discovered by Anders Gustaf Ekeberg , in 1802 . It is a rare, hard, blue-
gray, and lustrous transition metal, with the symbol Ta. These interesting elements are
chemically similar and are associated with each other in nature. Separaton of niobium
from tantalum was very difficult due to the chemical similarities of their oxides and due to
their nearly identical atomic radii. For many years, the commercial technology for
separating tantalum from niobium involved the fractional crystallization of potassium
heptafluorotantalate away from potassium oxypentafluoroniobate monohydrate, a
process discovered by Jean Charles Galissard de Marignac in 1866. There are yet a few
others that have been tested only on a laboratory scale. All these processes can
essentially be divided into reduction to metallic or compound form, chlorination, alkaline
fusion and acid dissolution.

One of the simplest methods for the breakdown treatment of primary concentrates of
niobium and tantalum, particularly pyrochlore and columbite-tantalite, is direct reduction
with aluminum or carbon, with or without the addition of iron or iron oxides termed
aluminothermic and carbothermic reduction reaction. Aluminothermic reduction reaction
is highly exothermic and is thermodynamically feasible even at room temperatura.

Chlorination is a process for breakdown of ores and concentrates of many of the refractory
metals, and even some of the commonly used metals are very attractive, an important
features of chlorination, include the high reactivity of chlorine, relative ease in gasifying
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many of the constituents of the concentrates due to high volatility of most of the chlorides,
and high water solubility of most of the chlorides.

The chlorides formed can also be readily separated due to differences in their vapour
pressures, or due to differences in reactivity with oxygen and/or water vapour and in their
reducibility with hydrogen.

A large number of alkaline fluxes, such as caustic soda, soda ash, caustic potash,
potassium carbonate, and a mixture of these, with or without addition of oxidizing agent
such as sodium nitrate and sodium peroxide have been used by a large number of
investigators.

Alkaline fusion in combination with acid leaching is one of the first methods to be adopted
on an industrial scale to achieve simultaneous breakdown of columbite and tantalite
concentrate and upgrading of niobium and tantalum values by leaching out of iron,
manganese, tin, titanium and silicon.

In industrial leaching, solvent and solids are mixed, allowed to approach equilibrium, and
the two phases are separated. Liquids and solids move counter currently to the adjacent
stages.

3. EXTRACTION AND SEPARATION OF NIOBIUM AND TANTALUM

3.1 Processes of Extraction and Separation

The first step in the processing is the reaction of the oxides with hydrofluoric acid. The
first industrial scale separation, developed by de Marignac, used the difference in
solubility between the complex niobium and tantalum fluorides, dipotassium
oxypentafluoroniobate monohydrate and dipotassium heptafluorotantalate in water.

The complex niobium and tantalum fluorides are extracted separately from the organic
solvent with water and either precipitated by the addition of potassium fluoride to produce
a potassium fluoride complex, or precipitated with ammonia as the pentoxide.

Several methods are used for the reduction to metallic niobium. The electrolysis of a
molten mixture of K2[NbOF5] and sodium chloride is one; the other is the reduction of the
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fluoride with sodium. With this method niobium with a relatively high purity can be
obtained.

To enhance the reaction, small amounts of oxidizers like sodium nitrate are added. The
result is aluminium oxide and ferroniobium, an alloy of iron and niobium used in the steel
production. The ferroniobium contains between 60 and 70% of niobium. Without addition
of iron oxide, aluminothermic process is used for the production of niobium. Further
purification is necessary to reach the grade for superconductive alloys.

3.2 Newer Processes of Extraction and Separation of Niobium and Tantalum

A scheme of a proposed model by Amuda is presented the next figure. The figure
incorporates mainly gravity, magnetic and electrostatic separation techniques with
leaching as adjunct beneficiation technique to generate the various secondary ore
concentrates.

Agulyanski reorted the use of 2-octanol for the separation of niobium and tantalum. The
process consists of the collective extraction of tantalum and niobium, scrubbing, niobium
stripping and Tantalum stripping.

El hussaini and Rice extracted niobium and tantalum from a leach liquor with tertiary
amine, Alamine 336, using kerosene and xylene as diluents and n-decanol as a modifier.
He investigated the effect of contact time, sulphate and fluoride concentrations in the
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aqueous phase, extractant concentration and aqueous to organic phase ratio. Both
elements were extracted to different extents, with tantalum extraction slightly greater. The
separation factor was greater for kerosene diluent.

Damodaran et al carried out solvent extraction studies of niobium and tantalum in Indian
with tributyl phosphate [TBP]. In his system niobium and tantalum were extracted together
from the flouride solution at high acidities, and subsequently selectively stripped from the
organic phase.

Conclusion:

The extraction and separation of niobium and tantalum by solvent extraction has proven
to be simple, rapid and very efficient. Solvent extraction is largely applied in the
purification processes in chemical and metallurgical industries and it likewise provides
selective extraction and recovery of niobium and tantalum from aqueous solution. This
present review also shows that the extraction and separation of niobium and tantalum
from their ores involves the breakdown treatment of the source, extraction and separation
by varying experimental conditions, precipitation, filtration, washing, drying and
calcinations. Other techniques such as gravity, magnetic and electrostatic separation
techniques may be coupled as adjunct to obtain a purer niobium and tantalum.
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Article IV: Review of hydrometallurgical recovery of zinc from industrial

wastes by M. K. Jha.

Zinc is an important base metal required for various applications in metallurgical, chemical
and textile industries. It is mainly recovered from primary sulphide concentrates. A part of
zinc is also recovered from different secondary resources viz. zinc ash, zinc dross, flue
dusts of electric arc furnace and brass smelting, automobile shredder scrap, rayon
industry sludge etc. which contain different level of impurities depending on their sources.
The material could be used to recover metallic values or it may be disposed off. But, the
disposal of such materials is now becoming expensive because of increasingly stringent
environmental protection regulations.

The toxicity is mainly due to the presence of different metals viz. lead, cadmium, arsenic,
chromium etc.

The hydrometallurgical processes are more environmentally suitable and economical to

treat even low zinc containing materials on small scale. It can process secondaries
containing different impurities. In this paper, a review has been made for the recovery of
zinc from the different secondaries/wastes containing zinc using different lixiviants.

Zinc ash is obtained in the dry galvanizing process due to the oxidation of molten zinc on
top of the bath and floats on the surface of the molten zinc.

In galvanizing plant the zinc dross is usually a scum which floats on the surface.
Galvanisers dross, on the other hand, is a material consisting of an alloy of Fe and Zn
which usually settles at the bottom of the zinc bath. This is formed by the reaction of
molten zinc with the steel kettle wall and the steel article. The usual composition of the
dross is 96% zinc and 4% iron.

Zinc dusts from the smelting operation are generated in the electric arc furnace (EAF)
where different types of scrap are charged in the furnace for the production of steel. These
scraps contain different non-ferrous metals. During smelting of these materials, zinc metal
along with other metals get evaporated and condensed during cooling.
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Blast furnace flue dusts are mixture of oxides discharged from the top of the blast furnace,
whose major components are iron oxides. The dusts also contain zinc, silicon,
magnesium and other minor element oxides in lesser amounts and in some cases volatile
elements viz. zinc, cadmium, chromium and arsenic.

In hydrometallurgical processing of zinc sulphide concentrate, zinc containing leach

residue, purification residue, beta cake, pot skimming etc. are generated in different
processing operations. The leach residue is obtained during the leaching of the roasted
sulphide concentrate in dilute sulphuric acid. This constitutes mainly iron and impregnated
zinc sulphate and zinc ferrite. It is considered as non-toxic waste.

Piret and Castel, 1990 analysed the suitability of a process for the treatment of
secondaries. The process selection is reported to depend on the physical properties and
the different constituents present in the material. Rabah and El-Sayed, 1995 stressed the
importance of particle size for metal recovery from dry cell battery, zinc dross and zinc
ash using pyrometallurgical and hydrometallurgical processes. Barrera, 1992 treated
electric arc furnace dust (EAFD) for the recovery of zinc following pyro-hydrometallurgical
method.

The electric arc furnace dusts (EAFD) have been extensively studied using sulphuric acid
as lixiviant for zinc recovery. Problems were encountered in filtering due to presence of
high concentration of iron (20–22 g/l) in the solution.

During hydrometallurgical processing, undesired species are also dissolved along with
the metal of interest in the solution. These impurities are removed by selective
precipitation, cementation, solvent extraction, ion exchange or electrolysis methods. In
selective precipitation a salt having low solubility is precipitated. Iron is removed by
controlling the pH of the leach solution. In the cementation process, the electromotive
force series is used to selectively cement out the more electropositive element using
electronegative element. Thus, the cadmium and copper are removed from the solution
with use of zinc metal in sulphate solution.