New Era Pressure Hydrometallurgy

4. Leaching in absence of oxygen

Fathi Habashi Laval University, Quebec City, Canada Fathi.Habashi@arul.ulaval.ca

Bauxite

Aluminum minerals in bauxite are soluble in dilute H2SO4 but this process is not used on large scale for the following reasons: Iron minerals and to some extent titanium minerals are also soluble; this will lead to an excessive reagent consumption and solution purification problem later. Al(OH)3 precipitated from acid solutions is gelatinous and difficult to filter and wash. Acid leaching is used only on a small scale to produce aluminum sulfate needed for water treatment.

Bayer process

Leaching of Bauxite

Al(OH)3 + OH [Al(OH)4] AlOOH + OH [AlO(OH)2]

 Sometimes NaOH is formed in situ in the autoclaves by adding sodium carbonate and calcium hydroxide: Na2CO3 + Ca(OH)2 2NaOH + CaCO3

BAUXITE Grushing Washing

Bayer Process

NaOH NaOH make-up

Drying Grinding

Leaching Settling Water Dilution Thickener Filtration Seed Precipitation Filtration Evaporation Centrifuge Recycle Solid impurities Washing Calcination Pure Al 2O 3 Red mud Red mud Sand

Red mud

Bauxite % Al2O3 SiO2 Fe2O3 TiO2 Na2O Loss on ignition 57.8 3.5 24.3 2.5 12.5

Red mud (dried at 105C) % 14.0 7.6 57.6 5.7 7.4 7.7

Calcined Al2O3 % 99.55 0.05 0.04 0.18 0.18

g/100 g free Na2O Al2O3 CaO Fe2O3 Ga2O3 Na2O SiO2 TiO2 32.80 0.12 0.05 0.22 100.00 0.60 Trace Cl CO2 F MgO P2O5 SO3 V2O5 1.00 3.74 0.03 0.17 0.90 0.07 0.45

Silicon
Silicon occurs as quartz, SiO2, or as clays, e.g., kaolinite, Al2(OH)4(Si2O5). Quartz is insoluble in NaOH under the conditions of leaching but the silicates are soluble. During digestion, silica that goes into solution combines with alumina and sodium hydroxide forming insoluble hydrated aluminosilicates such as 2Na2O2Al2O33SiO22H2O, which are carried away in the red mud, thus causing losses. About 1 kg of NaOH is lost for each kilogram of soluble silica in bauxite. Although most of the soluble silica in bauxite is precipitated during digestion by forming sodium aluminosilicate, small amounts may still be found in solution, especially when concentrated NaOH solution is used.

 To precipitate the silica completely, addition of CaO is recommended, since insoluble calcium silicate can be formed. Lime addition during digestion has a further advantage: any Na2CO3 present in the solution due to absorption of CO2 from the atmosphere, and which has no dissolving action on bauxite, will be converted to NaOH.

Gallium
Gallium occurs in most bauxites, and is highest in French bauxites (0.00.05% Ga2O3). It dissolves completely during extraction. Recycling of NaOH in the process results in gallium enrichment up to 0.5 g/L. Such liquors are therefore an important source of gallium, from which it can be recovered, e.g., by solvent extraction or electrolysis using a mercury cathode.

Vanadium
Vanadium in bauxite is partly soluble during digestion. In some ores it is precipitated during evaporating the leach solution as complex salts such as 2Na3VO4NaF19H2O. This is especially the case for ores containing fluorine since fluorides are dissolved during leaching. Sometimes these precipitate to form a hard scale in the evaporators which interferes with heat transfer. In other ores vanadium builds up in the recycle NaOH to a concentration of about 0.5 g/L V2O5 and is recovered.

Kaolinite
Kaolinite is the most important mineral in clays. North America produces about 50% of the worlds aluminum, yet must import more than 90% of the raw material needed, although there is abundant domestic resources of aluminumbearing silicates raw materials such as clay, shale, anorthosite, nepheline, and fly ash from power plants. That is why there is extensive research underway to recover alumina from these nonbauxitic sources.

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Bauxite Clay Shale % % % Al2O3 5560 SiO2 3.5 Fe2O3 225 TiO2 15 CaO 0.20.6 MgO Na2O 0.02 + K2O H2O 1030 34 45 2.6 2.4 23 58 6 1 2 5 215

Anorthit Nepheline Fly ash e % % % 2035 45.55 13 <1 515 1 18 <1 2328 45.60 13 0.2 13 0.1 46 trace 2432 4551 711 1 15 14 1030 nil

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Russia has the only aluminum industry based partly on non-bauxite raw materials, namely a nepheline syenite that contains apatite in the Kola Peninsula. This operation was possible because of the large production of apatite for fertilizer, and the production of Portland cement as a co-product

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Dehydroxylation at 400C
Al2(Si2O5)(OH)4 Al2O3.2SiO2 + 2H2O

Process H2SO4 HCl HNO3

Cost of acid Low Medium High

Decomposition reaction Al2(SO4)318H2O Al2O3 + 3SO3 + 18H2O 2AlCl3.H2O Al2O3 + 6HCl + 9H2O 2Al(NO3)39H2O Al2O3 + 6HNO3 + 15H2O

Energy needed for decomposition High Medium Low

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Pressure leaching of clay

All attempts to apply this technology cannot compete with Bayer process. . All this may change in the future. Researchers at the former US Bureau of Mines extracted alumina from un-calcined kaolinitic clay in 15 minutes by heating at 200oC using 20-27% HCl at 20% excess to the stoichiometric amount: A12O3.2SiO2.2H2O + 6HCl 2AlCl3 + 2SiO2 + 5H2O

Orbite process

HCl
Clay
Aluminum chloride

Iron chloride

crystalization Leaching Solid/liquid separation Silica crystalization HCl Calcination Al2O3

Calcination

Fe2O3

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 An advantage of the new technology is that silica is produced which can be considered as a byproduct while red mud from bauxite is a waste product.

Laterites

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Laterite leaching plants in Western Australia

Murrin Murrin

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Ramu laterite plant in Madang in the Papua New Guinea

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Ramu laterite plant in Madang in the Papua New Guinea

One of the three large autoclaves being transported from China to Madang

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Ambatovy mine in Madagascar

Autoclaves at Ambatovy

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Production of nickel, cobalt, and ammonium sulfate in Madagascar

Processing of Ilmenite
Pyrometallurgical method. Partial reduction with anthracite in an electric furnace to get cast iron and a slag rich in titanium. Titanium slag in mainly iron magnesium titanate, (Fe,Mg)Ti4O10, and a small amount of silicates Hydrometallurgical method. Leaching of iron oxide and obtaining a residue rich in titanium (9095% TiO2) known as synthetic rutile. The slag and synthetic rutile can then be processed to TiO2 pigment or titanium metal.

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Conc. H2SO4

Ilmenite

Baking H2O

Leaching of Ilmenite
FeTiO3 + 4H+ Fe2+ + TiO2+ + 2H2O

Leaching Filtration Crystallization Centrifuge Seed Hydrolysis Filtration Dilute H2SO4 FeSO4 4H2O H2O Residue

Drying Calcination TiO2

Titanium Raw Materials

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Synthetic Rutile
FeTiO3 + 2H+ TiO2(impure) + Fe2+ + H2O
HCl Ilmenite Digestion Filtration Oxyhydrolysis Fe2O3 Synthetic rutile

Oxyhydrolysis of FeCl2

2FeCl2 + 2H2O + O2 Fe2O3 + 4HCl

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Conc. H2SO4

Titanium slag Baking

Processing of Titanium Slag

H2O Leaching Filtration Seed Hydrolysis Filtration Dilute H2SO4 Residue H2O

Drying Calcination TiO2

Niobium & Tantalum

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 Columbite, tantalite, and pyrochlore are mainly used to prepare ferroniobium and ferrotantalum by pyrometallurgical methods To prepare metallic niobium and tantalum a pure oxide is usually prepared first by treating the concentrates by hydrometallurgical methods Tin slags, especially those from Malaysia and Thailand, were at one time an important source of niobium, tantalum, as well as tungsten.

Pyrochlore can also be beneficiated to a product containing 9097% Nb2O5 by reaction with 36% HCl at 200C and about 1000 kPa for 4 hours in a pressure reactor. The reaction is based on the formation of the niobium ion which hydrolyses to Nb2O5 at the reaction temperature. The reaction takes place in two consecutive steps:
3(Nb2O5.CaO) + 2HC1 2Nb2O5 + Ca2Nb2O7 + CaC12 + H2O pyrochlore Ca2Nb2O7 + 4HC1 Nb2O5 + 2CaC12 + 2H2O

Calcium niobate, Ca2Nb2O7, is formed as a non-porous intermediate product on the pyrochlore grains through which the reactant and the products must diffuse.

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WOLFRAMITE AND SCHEELITE

Wolframite, (Fe,Mn)WO4 or (Fe,Mn)O.WO3 Scheelite, CaWO4 or CaOWO3

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Acid digestion
Sulfuric should not be used

Alkaline Digestion

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Plant for pressure leaching of tungsten concentrate

ARSENIDES AND ANTIMONIDES The presence of arsenic and antimony in sulfide concentrates is undesirable because these metals complicate the smelting and refining. As a result there is interest to remove them before smelting. One route is leaching the concentrate by an alkaline sodium sulfide solution at high temperature and pressure.

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Purification of chalcopyrite concentrate

A copper sulfide concentrate containing 4% As and 7% Sb was treated in British Columbia by Equity Silver Company by this method. The finely divided concentrate is leached for 16 hours at 110C to solubilize arsenic and antimony sulfides: As2S3 + 3S2 2AsS33 Sb2S3 + 3S2 2SbS33 After filtration, the copper concentrate is shipped to smelters.

The leach solution contains 30 g/L As and 53 g/L Sb. It can be treated in two ways: Electrolyzed in a diaphragm cell to get antimony and regenerate the leach solution: Treated with oxygen in autoclaves at 150C and 550 kPa to decompose the antimony thiocomplex:
Na3SbS3 + 4NaOH + H2O + 13/2O2 NaSb(OH)6 + 3Na2SO4 SbS32 + 4e Sb + 3S2

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 In a similar way complex cassiterite, SnO2, concentrate especially those from Bolivia was purified by boiling at 110oC with HCl in autoclaves to remove impurities. This was conducted in rotating spherical autoclaves at the Longhorn Smelter in Texas. This resulted in removing most of the impurities and the tin oxide obtained was amenable to conventional smelting.

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