PART 1 Principles of metal extraction

a) The occurrence of metals in the Earth's crust Metals are found in the Earth's crust. The least reactive metals are found as elements (i.e. native, e.g. silver, gold), but most metals are found in compounds, usually oxides or sulphides. Rocks that contain a high enough percentage of a metal to be extracted commercially are known as ores (what percentage is required depends on the value of the metal). Aluminium and iron are the most abundant metals in the Earth's crust, and they are widely distributed around the world, which explains why they are so widely used. There are some other commonly used metals, such as nickel and copper that are scarce in the Earth's crust, but occur in high grade ores in a few locations.

2) Methods of extraction Most compounds are found as oxides or sulphides. Sulphides are converted to oxides by roasting in air. e.g. ZnS + /2 O2 ZnO + SO2
3

Roasting sulphide ores produces sulphur dioxide which could lead to acid rain. However, the sulphur dioxide formed can be collected and used to manufacture some sulphuric acid. SO2 + H2O + O2 H2SO4

The extraction of metals involves reduction. In these reactions, the metal ions gain electrons (e.g. Fe Na). There are a number of different methods of metal extraction, including: by heating with carbon (in the form of coke) by heating with a more reactive metal (active metal) by electrolysis of melts by reduction with hydrogen gas

3+

Fe, Na

Which method is used depends on: 1) the energy requirements 2) the cost of the reductant 3) the metal purity required extraction uses large amounts of energy (electricity and / or heat) carbon (in the form of coke), which is cheap, is widely used, but sometimes more reactive metals are required which are very costly the higher the required purity, the greater the cost in obtaining that purity

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Chemsheets AS 045

PART 2 Examples of metal extraction

a) Carbon reduction (e.g. Fe, Mn, Cu) Carbon is a cheap and plentiful reducing agent. It is often used in the form of coke (which is made by heating coal in the absence of air). In theory all metals can be extracted this way, but for some the temperature required is excessively high (and so uneconomic) metal carbides are formed rather than the metal itself (e.g. aluminium, tungsten, titanium)

Carbon reduction tends to be used for less reactive metals (e.g. iron).

i)

Extraction of iron Heamatite is the main ore of iron and contains Fe2O3. The iron is reduced by carbon and carbon monoxide in a continuous process.

Coke is burned in hot air, producing CO2 and a lot of heat (needed for all the other reactions). In the high temperatures in the furnace, more coke is reacted with the carbon dioxide produced, forming CO. The iron oxide is reduced to iron by the CO and some C (due to the heat the iron is molten, and so can be run off). In the hottest parts of the furnace, carbon itself reduces the iron oxide to iron. Limestone is used to remove sandy impurities from the ore, reacting to form slag (which is used in road making).

C + O2 CO2
iron oxide, coke and limestone

C + CO2 2 CO
waste gases

Fe2O3 + 3 CO 2 Fe + 3 C

Fe2O3 + 3 C 2 Fe + 3 CO
molten slag hot air molten iron

ii) Extraction of manganese Manganese is formed from the reduction of manganese (IV) oxide with carbon: MnO2 + C Mn + CO2

iii) Extraction of copper Malachite contains CuCO3 which on heating forms copper (II) oxide. Copper can be formed from the reduction of copper (II) oxide with carbon: CuCO3 CuO + CO2 2 CuO + C 2 Cu + CO2

Not much copper is made this way as newer alternative methods from aqueous solutions have been developed which have environmental advantages (see later).

b) reduction by hydrogen (e.g. W) Tungsten cannot be extracted with carbon because tungsten carbide (WC) is formed rather than tungsten. Tungsten (VI) oxide (WO3) is heated with hydrogen at 900C. WO3 + 3 H2 W + 3 H2O There are risks with using hydrogen that must be carefully managed.

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c) electrolysis of melts(e.g. Al) For some metals for which reduction with carbon is unsuitable, electrolysis of melts may be used. Aluminium is a good example. The raw materials for the extraction of aluminium are purified aluminium oxide (Al2O3) and cryolite (Na3AlF6). The aluminium oxide must be molten or dissolved to conduct electricity, and so is dissolved in molten cryolite (this requires a lower temperature than using molten aluminium oxide so has lower energy costs). The electrodes are made of graphite. This is a continuous process.
graphite positive electrode 2 O2- - 4 e- O2 molten mixture of aluminium oxide and cryolite

graphite negative electrode Al3+ + 3 e- Al

molten aluminium

The positive electrode burns due to the oxygen produced there (forming carbon dioxide), and so the positive electrode has to be replaced frequently. The main cost in this process is the electricity so a cheap supply is needed plants are often built near hydroelectric power stations.

d) reduction by active metal (e.g. Ti) Titanium cannot be extracted with carbon because titanium carbide (TiC) is formed rather than titanium. Titanium is a very useful metal as it abundant, has a low density and is corrosion resistant it is used for making strong, low density alloys for use in aircraft for example. Titantium has be very pure to have these useful properties and so electrolysis is not suitable. The metal is extracted by reaction with a more reactive metal (e.g. Mg, Na). The main ore is rutile, containing TiO2. 1) TiO2 (solid) is converted to TiCl4 (liquid) at 900C: 2) The TiCl4 is purified by fractional distillation in an Ar atmosphere. 3) The Ti is extracted by Mg or Na in an Ar atmosphere at 1000C: TiCl4 + 4 Na Ti + 4 NaCl TiCl4 + 2 Mg Ti + 2 MgCl2 TiO2 is converted to TiCl4 as it can be purified by fractional distillation, TiCl4 being molecular (liquid at room temperature) rather than ionic like TiO2 (solid at room temperature). The process is expensive due to the heat, the Na/Mg, the Ar, and the fact that it is a batch process. TiO2 + 2 Cl2 + 2 C TiCl4 + 2 CO

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Chemsheets AS 045

PART 3 Environmental aspects of metal extraction

a) Recycling metals We need to recycle metals as supplied will not last for ever (for some metals this would happen in our lifetimes). Recycling metals: saves resources (e.g. metal ores) creates less waste (e.g. mining waste) saves energy resources (less energy to re-cycle than make from ore, e.g. recycling Al uses 5% of energy used to extract) reduces air pollution (e.g. CO2 greenhouse effect, SO2 acid rain, CO - toxic)

However, there are costs associated with sorting and transporting metals to be recycled that have to be factored into the overall financial and energy costs.

b) Recycling copper One way to recycle copper is to react scrap copper with sulphuric acid or a specific enzyme to form solutions 2+ containing Cu (aq). The copper can be extracted by reaction with scrap iron: Cu (aq) + Fe(s) Cu(s) + Fe (aq)
2+ 2+

This method can also be used to extract copper from low grade ores.

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10-Jul-12

Chemsheets AS 045