Smelting

Smelting is a process of applying heat and a chemical reducing agent to an ore to extract a desired base metal product. It is a form of [extractive metallurgy](/wiki/extractive-metallurgy) that is used to obtain many metals such as iron, copper, silver, tin, lead, and zinc. Smelting uses heat and a chemical reducing agent to decompose the ore, driving off other elements as gases or slag and leaving the metal behind. The reducing agent is commonly a fossil-fuel source of carbon, such as carbon monoxide from incomplete combustion of coke—or, in earlier times, of charcoal. The oxygen in the ore binds to carbon at high temperatures, as the chemical potential energy of the bonds in carbon dioxide (CO2) is lower than that of the bonds in the ore.

Sulfide ores such as those commonly used to obtain copper, zinc, or lead, are roasted before smelting in order to convert the sulfides to oxides, which are more readily reduced to the metal. Roasting heats the ore in the presence of oxygen from air, oxidizing the ore and liberating the sulfur as sulfur dioxide gas.

Smelting most prominently takes place in a blast furnace to produce pig iron, which is converted into steel. Plants for the electrolytic reduction of aluminium are referred to as aluminium smelters.

Smelters can be classified into two types depending on their business model; custom smelters and integrated smelters. A custom smelter is a smelter that treats ore on behalf of customers or buys ore for treatment. Custom smelters obtain ore concentrates from mines of different ownership. Integrated smelters depend directly on a specific mining operation and tend to be located next to a mine.

Source: Wikimedia Commons, CC BY 2.0

Process

Smelting involves more than just melting the metal out of its ore. Most ores comprise chemical compounds of the metal and other elements, such as oxygen (as an oxide), sulfur (as a sulfide), or carbon and oxygen together (as a carbonate). To extract the metal, workers must make these compounds undergo a chemical reaction. Smelting, therefore, consists of using suitable reducing substances that combine with those oxidizing elements to free the metal.

Roasting

In the case of sulfides and carbonates, a process called "roasting" removes the unwanted carbon or sulfur, leaving an oxide, which is more suitable for reduction to metal. Roasting is usually carried out in an oxidizing environment. A few practical examples:

For sulfide ores, roasting results in replacement of sulfide, partly or completely, by oxide. For molybdenum disulfide, the main ore of Mo, roasting proceeds as follows:

MoS2 + 3O2 → MoO2 + 2 SO2

Reduction

Reduction is the final, high-temperature step in smelting, in which the oxide becomes the elemental metal. A reducing environment (often provided by carbon monoxide, made by incomplete combustion in an air-starved furnace) pulls the final oxygen atoms from the raw metal. The carbon source acts as a chemical reactant to remove oxygen from the ore, yielding the purified metal element as a product. The carbon source is oxidized in two stages. First, carbon (C) combusts with oxygen (O2) in the air to produce carbon monoxide (CO). Second, the carbon monoxide reacts with the ore (e.g. Fe2O3) and removes one of its oxygen atoms, releasing carbon dioxide (CO2). After successive interactions with carbon monoxide, all of the oxygen in the ore will be removed, leaving the raw metal element (e.g. Fe). As most ores are impure, it is often necessary to use flux, such as limestone (or dolomite), to remove the accompanying rock gangue as slag. This calcination reaction emits carbon dioxide.

The required temperature varies both in absolute terms and in terms of the melting point of the base metal. Examples:

Iron oxide becomes metallic iron at roughly 1250 °C (2282 °F or 1523 K), almost 300 degrees below iron's melting point of 1538 °C (2800 °F or 1811 K).

Mercuric oxide becomes vaporous mercury near 550 °C (1022 °F or 823 K), almost 600 degrees above mercury's melting point of -38 °C (-36.4 °F or 235 K), and also above mercury's boiling point.

Fluxes

Fluxes are materials added to the ore during smelting to catalyze the desired reactions and to chemically bind to unwanted impurities or reaction products. Calcium carbonate or calcium oxide in the form of lime are often used for this purpose, since they react with sulfur, phosphorus, and silicon impurities to allow them to be readily separated and discarded, in the form of slag. Fluxes may also serve to control the viscosity and neutralize unwanted acids.

Flux and slag can provide a secondary service after the reduction step is complete; they provide a molten cover on the purified metal, preventing contact with oxygen while still hot enough to readily oxidize. This prevents impurities from forming in the metal.

Sulfide ores

The ores of base metals are often sulfides. In recent centuries, reverberatory furnaces have been used to keep the charge being smelted separately from the fuel. Traditionally, they were used for the first step of smelting: forming two liquids, one an oxide slag containing most of the impurities, and the other a sulfide matte containing the valuable metal sulfide and some impurities. Such "reverb" furnaces are today about 40 meters long, 3 meters high, and 10 meters wide. Fuel is burned at one end to melt the dry sulfide concentrates (usually after partial roasting) which are fed through openings in the roof of the furnace. The slag floats over the heavier matte and is removed and discarded or recycled. The sulfide matte is then sent to the converter. The precise details of the process vary from one furnace to another depending on the mineralogy of the ore body.

While reverberatory furnaces produced slags containing very little copper, they were relatively energy inefficient and off-gassed a low concentration of sulfur dioxide that was difficult to capture; a new generation of copper smelting technologies has supplanted them. More recent furnaces exploit bath smelting, top-jetting lance smelting, flash smelting, and blast furnaces. Some examples of bath smelters include the Noranda furnace, the Isasmelt furnace, the Teniente reactor, the Vunyukov smelter, and the SKS technology. Top-jetting lance smelters include the Mitsubishi smelting reactor. Flash smelters account for over 50% of the world's copper smelters. There are many more varieties of smelting processes, including the Kivset, Ausmelt, Tamano, EAF, and BF.

History

Of the seven metals known in antiquity, only gold regularly occurs in nature as a native metal. The others – copper, lead, silver, tin, iron, and mercury – occur primarily as minerals, although native copper is occasionally found in commercially significant quantities. These minerals are primarily carbonates, sulfides, or oxides of the metal, mixed with other components such as silica and alumina. Roasting the carbonate and sulfide minerals in the air converts them to oxides. The oxides, in turn, are smelted into the metal. Carbon monoxide was (and is) the reducing agent of choice for smelting. It is easily produced during the heating process, and as a gas comes into intimate contact with the ore.

In the Old World, humans learned to smelt metals in prehistoric times, more than 8000 years ago. The discovery and use of the "useful" metals – copper and bronze at first, then iron a few millennia later – had an enormous impact on human society. The impact was so pervasive that scholars traditionally divide ancient history into Stone Age, Bronze Age, and Iron Age.

In the Americas, pre-Inca civilizations of the central Andes in Peru had mastered the smelting of copper and silver at least six centuries before the first Europeans arrived in the 16th century, while never mastering the smelting of metals such as iron for use with weapon craft.

Source: Wikimedia Commons, Public domain

Copper and bronze

Copper was the first metal to be smelted. How the discovery came about is debated. Campfires are about 200 °C short of the temperature needed.