TECNOLÓGICO NACIONAL DE MÉXICO

INSTITUTO TECNOLÓGICO DE LA LAGUNA

HIDROMETALURGIA

UNIDAD 1

“TEMA I. ACTIVIDAD 2. TRABAJO DE

INVESTIGACIÓN”
Semestre: Agosto - Diciembre

Maestro: Simón Alberto Pedroza Figueroa

EQUIPO:

Ávila Zapata Arely Denisse N.C: 19131294

Cortez González Daniel Eduardo N.C: 17131078
García Carlos Ana Margarita N.C: 19131328
Muñoz Rede Jorge N.C: 19131372
Torres Blanco Ángel Guadalupe N.C: 19131417

Torreón, Coah. Fecha: 5 de SEPTIEMBRE del 2022

 A short history of hydrometallurgy

1. Introduction

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 when acids and alkalines became known and used.

2. Roots

The roots of hydrometallurgy may be traced back to the period of alchemists when the
transmutation of base metals into gold was their prime occupation. The discovery of aqua
regia by Jabir Ibn Hayyan, an Arab alchemist, may be considered as a milestone marking
the beginning of hydrometallurgy. Aqua regia, i.e., royal water, is a 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.

In the 16th century, the extraction of copper by wet methods received some attention.
Heap leaching was practiced in Germany and 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”.
 3. The beginnings
The birth of modern hydrometallurgy dates back to 1887 when two important processes
were invented. The first, the cyanidation process for treating gold ores, and the second,
the Bayer Process for the production of alumina.

 Cyanidation process
The dissolving action of cyanide solution on metallic
gold was proposed and patented in England by John
Stewart MacArthur (1856–1920) in 1887 and
became known as the cyanidation process.

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.

Huge filtration plants designed to obtain clear leach

solutions for metal recovery were constructed.
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 the process, the
theory still remained lagging behind. As a result of
introducing the cyanidation process worldwide, gold
production increased greatly during the period 1900–
1910.
 Bayer process
The second major hydrometallurgical process of this era was the process invented
by Karl Josef Bayer for the preparation of pure Al2O3 and known as the Bayer
Process. This process 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 Al 2O3.

Bayer 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 hydroxide was used as a mordant in
dyeing cotton.
 Bayer’s first contribution was in 1887 when he discovered that
Al(OH)3 precipitated from alkaline solution was crystalline.
 A few years earlier to Bayer’s invention, Louis Le Chatelier (1815–
1873) in France described a method for making Al2O3 by heating
bauxite with Na2CO3 at 1200 °C.
 4. Further development
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.
Towards the beginning of the 20th century, hydrometallurgy of copper received a
particular attention. Oxide ores were leached on large scale by dilute sulfuric acid in Chile.

The First World War (1914–1918) created a demand

for the zinc for the manufacture of cartridge brass, this
situation inspired industry in North America to supply
additional metal from ores that were not amenable to
standard methods, the process 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. Létrange in France issued in 1881. Cadmium gradually emerges as an important by-
product of this process.

5. Development during World War II

In the 1940s, the technology of uranium production was introduced in connection with
the Manhattan Project. 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.

Separation of the rare earths by ion exchange replaced the tedious fractional
crystallization from solution. Later on, solvent extraction replaced ion Exchange.
 6. Recent advances
In the 1950s, pressure hydrometallurgy was introduced for leaching sulfide concentrates
(Sherritt-Gordon process), for laterites (Moa process) for tungsten ores, as well as for the
direct precipitation of metals from solution.

In the late 1950s work at the Mines Branch in Ottawa (known today as CANMET)
demonstrated that pyrrhotite– penthandite concentrate could be treated in autoclaves at
120°C under oxygen pressure to get nickel in solution while Fe 2O3 and elemental sulfur
remain in the residue.
The process was later applied by the Russians at the Norilsk plant for nickel recovery.

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 grader uranium and gold ores.

In the 1970s the pressure leaching of zinc sulfide concentrates was applied industrially in Canada.
The new process, which is essentially the same as that shown in Fig. 9, rendered the production of
zinc a fully hydrometallurgical process. The process has also the advantage of liberating the zinc
industry form the necessity of producing sulfuric acid.

In the 1980s, 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.

7. Conclusion
At present, about 20% of the cooper is now produced by hydrometallurgical technique.
Hydrometallurgy is a process that has become important over the years. Many metal
recovery processes apply hydrometallurgy, so their knowledge is essential.
A Review of Niobium-Tantalum Separation in Hydrometallurgy

1. Introduction
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. Is used in superconducting
magnets, commemorative coins, medical device, jewelries, arc-tube seals, capacitors,
optical lens, barometer and nuclear applications.

Tantalum was discovered by Anders Gustaf Ekeberg, in 1802. It is a rare, hard, blue-gray,
and lustrous transition metal, with the symbol Ta. Is used in alloys and wires, surgical
instruments, reaction vessels and pipes, ultra-high frequency electron tubes, lens, vacuum
furnace parts, watches and tantalum being chemically inert is also used in capacitors as
platinum substitute.

2. Breakdown treatment for primary sources

There are yet a few chemical treatment procedures 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.

2.1. Reduction

One of the simplest methods, 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.

2.1.1. Aluminothermic and carbothermic reduction reactions

During this process, all the oxides that have free energy of formation less negative
than that of alumina are reduced to metallic state and join the ferroalloy.

The carbothermic reduction reaction, is thermodynamically feasible at high

temperatures over 1500°C. Also, niobium and tantalum react with excess carbon and
form carbides.
2.2. Chlorination

Is a process for breakdown of ores and concentrates of many of the refractory metals, an
important features of chlorination, include the high reactivity of chlorine. 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. Thus, chlorination process is suitable not only for breakdown of the ore or
concentrate but also for the separation/purification of various elements co-occurring in
the concentrate and for reduction to metallic form.

2.3. Alkaline Fusion

This one is also one of the processes used for the breakdown of mineral ores concentrate.

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.

2.4. Leaching

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. The solvent phase, becomes more concentrated as it contacts in the stagewise
fashion the increasingly solute-rich solids. The raffinate becomes less concentrated in
soluble material as it moves towards the fresh solvent phase.

3. Extraction and separation of niobium and tantalum

3.1. Processes of Extraction and Separation

After the breakdown treatment, the mixed oxides of tantalum Ta 2O5 and niobium Nb2O5
are obtained. The first step in the processing is the reaction of the oxides with hydrofluoric
acid:
 Ta2O5 + 14HF  2H2[TaF7] + 5H2O

Nb2O5 + 10 HF  2H2[NbOF5] + 3H2O

Newer processes use the liquid extraction of the fluorides from aqueous solution by
organic solvents like: Octanol, bis(2-ethylhexyl) phosphoric acid (DEHPA), Alamine 336,
methyl isobutyl ketone (MIBK), tri-n-butyl phosphate (TBP) or cyclohexanone.

In the process involving the aluminothermic reaction a mixture of iron oxide and niobium
oxide is reacted with aluminium:

3Nb2O5 + Fe2O3 + 12Al → 6Nb + 2Fe + 6Al2O3

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.

Electron beam melting under vacuum is the method used by the two major distributors of
niobium.

3.2. Newer Processes of Extraction and Separation of Niobium and

Tantalum

Ilustración 1. Proposed Multi-Ore Constituent Concentration Model.

The process consists of the collective extraction of tantalum and niobium, scrubbing,
niobium stripping and Tantalum stripping. He stated that sulphuric acid was added to
Ta2O5 (50-60g/l) and Nb2O5 (30g/l) solutions in order to obtain an optimal acidity level.

El hussaini and Rice,

investigated the effect of
contact time, sulphate and
fluoride concentrations in the
aqueous phase, extractant
concentration and aqueous to
organic phase ratio.

Illustration 2. Extraction of tantalum and niobium versus H2SO4 concentration.

The pure tantalum in the form of H2TaF7 was then finally stripped with de-mineralized
water. On completion of the extraction of tantalum, the aqueous raffinate was made up to
5.0N HF-9.0N H2SO4 and equilibrated with fresh TBP to extract the niobium. Niobium was
then stripped with de-mineralized water.

Htet and Kay, studied the extraction of niobium oxide from columbite-tantalite
concentrate of Thayet Kon Area in Nay Phi Taw using methyl isobutyl ketone. He reported
that columbite-tantalite concentrate was leached with a mixture of hydrofluoric acid and
sulfuric acid. The variation of acid concentration and leaching time were studied. In order
that he recovered niobium oxide from the pregnant solution, solvent extraction method
using MIBK was carried out. Two stages were employed:

By adding NH4OH to the pregnant solution, precipitation took place until pH 11 was
reached. The precipitate and sodium hydroxide were put in a porcelain crucible and was
placed in the muffle furnace. HCl digestion was necessary to remove impurities. The fused
mass from caustic fusion was put in a beaker and leached for ½ hr. Calcinations was
further performed for the production of pure niobium oxide.
Flow diagram for the extraction of niobium oxide as shown in figure:

Thakur reported that a solution containing tantalum and

niobium along with some impurities was subjected to
solvent extraction (SX) treatment using the extractant
MIBK or TBP.

Both niobium and tantalum extract at high

concentration of H2SO4 (>8N), but only tantalum
extracts at lower acidity (3N-8N).

Then ammonia was added to the aqueous solution

containing pure niobium to precipitate niobium oxide
hydrate. Oxide hydrate of niobium was then separated
by filtration, dried and calcined in heated chambers or
rotary furnaces. Niobium oxide thus obtained is of high
purity.

Thakur reported that extractants are amenable to

degradation due to high concentrations of acids.

Illustration 3. Flow Diagram for the Extraction of Niobium Oxide.

The acid solution was mixed thoroughly with MIBK (methyl-iso-butyl ketone) which
dissolves the tantalum and niobium compounds into the ketone while leaving impurities in
the aqueous solution.

The niobium was then stripped with dilute acid, and the tantalum subsequently extracted
by acid ammonium fluoride. For tantalum, the metal could be produced in powder form
by sodium reduction of the fluoride.

Kigoshi, also developed a nitrofluor process for the extraction of niobium and tantalum
from columbite. He reported that the nitrofluor process provides a method of dissolving
columbite in a non-aqueous inorganic solvent, purifying the niobium and tantalum,
separating them by a volatile separation technique. A niobium-tantalum separation was
made possible by utilizing the difference of volatility of the complex fluorides formed with
an HF-N2O3 azeotrope used for the disintegration of the ore.

Ilustración 4. Nitrofluor process for treating Nb and Ta ore.

A process used by The World Intellectual Property Organization, for the treatment of raw
material containing tantalum and/or niobium in which the raw material was processed by
a solution containing ammonium fluoride at the boiling point for not more than 10 hours,
the obtained mixture was leached using water or a solution containing ammonia at a
temperature below 100°C for not more than 1 hour. The obtained solution was filtrated
giving a main filtrate containing Ta205 and/or Nb205 and the filtrate was processed by a
solution of NH3 in not more than 30 minutes.

From the solution, oxide hydrates of niobium and tantalum respectively were released
and the released oxide hydrates were calcinated giving a product containing more than
99% niobium and tantalum, respectively.
4. Conclusion

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 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.