Natural Resources
There are four main regions or “spheres” from which raw materials are taken (Figure 6). These are the lithosphere (crust), the biosphere (plants, animals, bacteria), the hydrosphere (oceans and freshwater) and the atmosphere. Metals extraction relies almost entirely on the lithosphere for metal bearing raw materials. However, the industry also relies heavily upon each of the other spheres: the hydrosphere for water; the atmosphere for air, or oxygen (concentrated from the air), and; the biosphere, e.g. animal proteins and carbohydrates as additives in metal processing and bacteria used in biological leaching of sulfide ores. It is intriguing to ponder the astounding differentiation between metal compounds in the earth’s crust and the oceans. Only three metal ions are found in the oceans at any appreciable concentration: Na+, 0.47%; Mg+2 0.053%, and; Ca+2, 0.010%. Some very valuable metals occur at very low concentrations in the oceans, e.g. gold at ~1 μg/L (~1 part per billion), but as yet there are no economic methods of extracting these. Note too that the lithosphere includes that roughly ¾ of the Earth’s surface which is covered by the oceans. This is largely unexplored. There is interest in this, but land-based mineral resources are still plentiful enough and economically much more viable. Oil and gas are notable exceptions.
Figure 6. Main terrestrial sources of raw materials.
How minerals are distributed in the earth’s crust is crucially important in the business of metal extraction. There are three aspects to this. One is the natural abundance of the element in the Earth’s crust. This is the average concentration in the lithosphere. A second is the occurrence of mineral deposits of the elements. Often these contain the pertinent minerals at considerably higher concentration than the average in the crust overall. It is fortunate that the elements are often not uniformly distributed. (Some elements are more evenly dispersed on average.) The third factor is that the mineral deposits must be able to be economically produced. The metals need to be present at suitable concentrations and in mineral forms that can be processed. Numerous factors go into the economic viability of a mineral deposit. To illustrate, copper has a natural abundance of 0.0068% by weight (68 g Cu per tonne of rock). But an economically producible copper mineral deposit would have contained around 1.8% Cu 100 years ago, whereas today a deposit with as little as 0.5% Cu could be economic to produce.
Table 1 shows the natural abundances of many commercially important metals and elements in the lithosphere. Most of the Earth’s crust is composed of oxygen (45.5%), silicon (27.2%), aluminum (8.3%), iron (6.2%), calcium, magnesium, sodium and potassium; these 8 elements comprise about 99% of the earth’s crust! Most of the transition metals and the other heavier metals are either rare or very rare, with a few exceptions (iron, titanium and manganese – among the earlier of the transition metals). Natural abundances are also illustrated in the form of a periodic table in Figure 7. Note that often the lighter elements are the more common, while the heaviest transition metals are relatively rare. Indeed the platinum group metals, gold and silver are among the very rarest elements. There are exceptions to the general rule. The lanthanides (also called the rare earths) are not actually all that rare, compared to some of the less abundant transition metals.
As mentioned previously, many elements are concentrated in mineral deposits. The major types of minerals are listed in Table 2. Where a mineral is a compound, it is commonly thought of as formally a combination of cations and anions. However, the nature of the bonds between the atoms is often a lot more complex than this. Components of ionic, covalent and metallic bonds, as well as weaker bonding interactions, like hydrogen bonding, may be involved. Hence one usually cannot regard minerals as actually being salts. PbS, for example, is formally comprised of Pb+2 and S2-, but in reality it is not composed of discrete cations and anions.
Table 1. Natural abundances in percent by weight of many commercially important metals and some non-metals in the Earth’s crust.
Li | Alkali Metals | Ni | 0.099 | Transition Metals |
Na | Pd | 1.5x10-6 | ||
K | Pt | 1x10-6 | ||
Be | Alkaline Earths | Cu | 0.0068 | |
Mg | Ag | 8x10-6 | ||
Ca | Au | 4x10-7 | ||
Sc | Transition Metals | Zn | 0.0076 | |
Y | Cd | 1.6x10-5 | ||
La | Hg | 8x10-6 | ||
Ti | Al | 8.3 | Groups III-VI | |
Zr | Ga | 0.0019 | ||
Hf | In | 2.4x10-5 | ||
V | Tl | 7x10-5 | ||
Nb | Sn | 0.00021 | ||
Ta | Pb | 0.0013 | ||
Cr | Bi | 8x10-7 | ||
Mo | Lanthanides | 8-660x10-5 | ||
W | Th | 0.00081 | Actinides | |
Mn | U | 0.00023 | ||
Re | Si | 27.2 | Semiconductors | |
Fe | Ge | 0.00015 | ||
Ru | As | 0.00018 | ||
Os | Sb | 2x10-5 | ||
Co | Te | 1x10-7 | ||
Rh | Se | 5x10-6 | ||
Ir | S | 0.034 | Non-metals |
Figure 7. Natural abundances of elements in the lithosphere.
Table 2. Classification of minerals according to their formally anionic components.
Mineral class | Anion |
---|---|
Sulfides | S2-, S22- (i.e. a polysulfide) |
Selenides, tellurides | Se2-, Te2- (rarer than sulfides) |
Oxides/hydroxides | O2-/OH-(common) |
Halides | Cl-, F-; rarely Br-, I- |
Carbonates | CO32- |
Sulfates | SO42- |
Nitrates | NO3- |
Phosphates | PO43- |
Arsenates | AsO43- |
Silicates | SiO44-, Si2O76-, many others (common) |
Aluminosilicates | [Alw(OH)xSiyOz]n- (numerous) |
Chromates | CrO42- |
Molybdates | MoO42- |
Tungstates | WO42- |
Vanadates | VO43- |
Borates | B(OH)4-, B4O5(OH)42-, etc. )others |
The formalism is useful for classification purposes and for understanding the chemistry. Minerals are usually classified by the formally anionic components since there are many metals that form precipitates with the same anion, for instance there are many metal sulfides, such as Cu2S, CuFeS2, PbS, ZnS, etc. In many cases the metal values reside in the formally cationic parts of the minerals, e.g. CuS (Cu+2/S2-), AlO(OH) (Al+3/O2-,OH–), and PbCO3 (Pb+2/CO32-). But in some cases the metal of interest resides in the formally anionic part as complex ions, e.g. CaWO4 (Ca+2/WO42-). Oxides/hydroxides, silicates/aluminosilicates and sulfides are the most commonly mined minerals. (There are also other classes of minerals which, in the context of metal production, are not commonly produced.)
A sample list of some of the more important minerals is shown below in
Table 3. Some rare and valuable metals may be disseminated in a variety of mineral matrices, for example gold may be hosted in quartz or pyrite or arsenopyrite etc. In some instances there are now few available ores of some metals (e.g. silver). In such cases the main means of production is as a by-product of another metal’s production. A partial list of applicable leaching systems for treating the mineral, or conditions under which it may at least partially be dissolved are also indicated in the table. Note the preponderance of acid, most often sulfuric acid (the cheapest of the “mineral acids”).
There are vastly more minerals than listed here, but this gives an indication of some of the more important ones. New minerals are still being discovered. Natural deposits may contain a diverse mixture of minerals, some at very low concentrations, which may have an impact on the extraction process. Thorough study of the mineralogy of an ore is crucial to a successful process. Many a plant has been doomed due to inattention to mineralogy.
In addition to minerals that contain metals of interest, ores inevitably contain gangue minerals. These have no commercial value in the context of the metal extraction process of interest. Very often the gangue constitutes by far the major fraction of an ore. This does not mean that some of the associated metals are not valuable. But, they cannot be economically processed from the given ore. For example, pyrite contains iron, the basis for steel, but there is not economically viable means to make iron from pyrite processed in the context of hydrometallurgy. Common gangue minerals and their reactivity are listed in Table 4.
Gangue minerals require careful attention. They may cause excessive consumption of costly reagents. They may host valuable minerals (e.g. fine crystals within gangue minerals, or chemical substituted within the gangue crystals, e.g. Ni in nickeliferrous limonite, Table 3). Gangue minerals may cause solid-liquid separation problems, e.g. clay minerals.
Table 3. Common and important minerals of various metals.
Metal | Mineral | Formula | Principal Leaching Chemistry |
---|---|---|---|
Al | Gibbsite Boehmite Diaspore Bauxite Corundum |
Al(OH)3 AlO(OH) AlO(OH) Mixtures of above 3 Al2O3 |
Caustic (NaOH) NaOH; less reactive than diaspore NaOH; less reactive than gibbsite NaOH; less reactive than boehmite |
Cu | Chalcopyrite
Chalcocite |
CuFeS2 Main Cu mineral Cu2S CuS Cu5FeS4 Cu2O Cu metal (rare) CuCO3·Cu(OH)2 2CuCO3·Cu(OH)2 CuO CuSiO3·2H2O 3CuO·CuCl2·3H2O Cu3AsS4 Cu3SbS3 |
HCl/oxidant, H2SO4/oxidant. Mainly treated by pyrometallurgy. H2SO4/oxidant H2SO4/oxidant H2SO4/oxidant H2SO4/oxidant H2SO4/oxidant; NH3/O2 Dilute H2SO4 Dilute H2SO4 Dilute H2SO4 Dilute H2SO4 Dilute H2SO4 Difficult to leach or smelt Difficult to leach or smelt |
Zn | Sphalerite Marmatite Zincite |
ZnS Main (Zn,Fe)S minerals ZnO (uncommon mineral; roasting ZnS -> ZnO; common) |
H2SO4/oxidant H2SO4/oxidant Dilute H2SO4 |
Fe | Magnetite Hematite Limonite Goethite Siderite Pyrite Marcasite Pyrrhotite Arsenopyrite |
Fe3O4 Fe2O3 FeO(OH)·nH2O FeO(OH) FeCO3 FeS2 (may bear Au) FeS2 Fe1-xS, 1-x ~ 1 FeAsS (may bear Au) |
Dilute acid Unreactive Acid (limonite may bear Ni) Acid (goethite may bear Ni) Dilute acid H2SO4/oxidant H2SO4/oxidant Acid or acid/oxidant |
Pb | Galena
Litharge |
PbS Main mineral; usually smelted PbO PbSO4 PbCO3 |
HCl/aq. Cl- salt/oxidant
HCl/aq. Cl- salt; HNO3 |
Ni | Pentlandite Garnierite Millerite Laterites, with nickeliferrous limonite |
(Ni,Fe)9S8 (Ni,Mg)6Si4O10(OH)8 NiS Complex oxides/silicates, |
H2SO4 or HCl/oxidant Strong H2SO4 H2SO4 or HCl/oxidant; NH3/O2 H2SO4; reductive roasting then leach with NH3/(NH4)2CO3 |
Co | Smaltite Cobaltite Linnaeite Laterites |
CoAs2 CoAsS Co3S4 CoS |
H2SO4 or HCl/oxidant As per Ni "Concentrate" formed from laterite leach; leach with NH3/O2 |
Sn | Cassiterite | SnO2 | Mainly by pyrometallurgy |
Ti | Ilmenite Rutile |
FeTiO3 TiO2 |
Very strong acids Very strong acids |
Mo | Molybdenite Molybdite Wulfenite Powellite |
MoS2 MoO3 PbMoO4 Ca(Mo,W)O4 |
Mainly by pyrometallurgy |
W | Scheelite Wolframite |
CaWO4 (Fe,Mn)WO4 |
HCl, H2SO4 NaOH |
Sb | Stibnite Jamesonite |
Sb2S3 FePb4Sb6S14 |
Generally undesirable impurities. May leach in acid/oxidant |
As | Realgar Orpiment |
As4S4 As2S3 |
Generally undesirable impurities. May leach in H2SO4/oxidant, cyanide/O2 systems |
Bi | Bismite Bismuthinite Native Bi |
Bi2O3 Bi2S3 Elemental Bi |
Acid/chloride Acid/oxidant Acid/oxidant |
Lanthanides (“Ln”) | Monazite | (La,Th,Ln)PO4 | Hot strong acid; NaOH |
U | Pitchblende | UO2.x; x < 0.67 |
H2SO4/oxidant; Na2CO3/oxidant |
Ag | Argentite Cerargyrite Native Ag |
Ag2S AgCl Ag metal |
CN-/oxidant; S2O32-/oxidant NH3; CN- CN-/oxidant |
Au | Native Au Calaverite Sylvanite |
Au metal AuTe2 (Au,Ag)Te2 |
CN-/oxidant; S2O32-/oxidant Hard to leach Hard to leach |
Hg | Cinnabar | HgS | Usually by pyrometallurgy |
PGM’s | Various and complex |
Table 4. Common gangue minerals. Superscripted Roman numerals, e.g. MII, refer to a formally +2 metal cation.
Mineral | Composition | Reactivity (Partial or Total Dissolution) |
---|---|---|
Quartz | SiO2 (may host gold) | Fluorides or strong NaOH |
Feldspars | M1-M2-Al-silicates M1, M2 = Na, K, Ca |
Relatively unreactive |
Mica, Chlorite | K2Al4(Si6Al2)O20(OH)4 Mg10Al2(Si6Al2)O20(OH)16 |
Dilute acids |
Amphiboles | MIIy-(Si4O11)(OH)x: many forms; MII = e.g. Ca, Mg, or both; includes asbestos |
Strong acids |
Clays | Layered aluminosilicates | Acids |
Pyroxene,
Olivine |
MIISiO3, (M1II,M2II)SiO3 MII, M1II, M2II = e.g. Ca, Mg (Mg,Fe)2SiO4 |
Acids |
Garnets,
Staurolite, |
M3IIM2III(SiO4)3 MII = e.g. Ca, Mg, Fe; MIII = e.g. Al, Cr, Fe (FeII,Mg,Zn)2Al9(Si,Al)4O22(OH)2 Al2SiO5 |
Relatively unreactive |
Andalusite, Sillimanite |
Al2SiO5 Al2SiO5 |
Acids |
Calcite | CaCO3 | Readily with dilute acids |
Magnesite, Dolomite |
MgCO3 CaMg(CO3)2 |
Acids |
Pyrrhotite | Fe1-xS, 1-x ~ 1 | Dilute acids; CN-/O2 |
Marcasite, Pyrite |
FeS2 FeS2 |
Acids/oxidants; CN-/O2 |
Magnetite Limonite Goethite Hematite |
Fe3O4 FeO(OH)·nH2O FeO(OH) Fe2O3 |
Acids (rates depend Acids on particle Acids size and crystallinity.) Practically unreactive |