Precious Metals Refining
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In
metallurgy Metallurgy is a domain of materials science and engineering that studies the physical and chemical behavior of metallic elements, their inter-metallic compounds, and their mixtures, which are known as alloys. Metallurgy encompasses both the ...
, refining consists of purifying an impure metal. It is to be distinguished from other processes such as
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 that is used to obtain many metals such as iron-making, iron, copper extraction, copper ...
and
calcining Calcination is thermal treatment of a solid chemical compound (e.g. mixed carbonate ores) whereby the compound is raised to high temperature without melting under restricted supply of ambient oxygen (i.e. gaseous O2 fraction of air), generally fo ...
in that those two involve a chemical change to the raw material, whereas in refining the final material is chemically identical to the raw material. Refining thus increases the purity of the raw material via processing. There are many processes including
pyrometallurgical Pyrometallurgy is a branch of extractive metallurgy. It consists of the thermal treatment of minerals and metallurgical ores and concentrates to bring about physical and chemical transformations in the materials to enable recovery of valuable ...
and hydrometallurgical techniques.


Lead


Cupellation

One ancient process for extracting the
silver Silver is a chemical element; it has Symbol (chemistry), symbol Ag () and atomic number 47. A soft, whitish-gray, lustrous transition metal, it exhibits the highest electrical conductivity, thermal conductivity, and reflectivity of any metal. ...
from
lead Lead () is a chemical element; it has Chemical symbol, symbol Pb (from Latin ) and atomic number 82. It is a Heavy metal (elements), heavy metal that is density, denser than most common materials. Lead is Mohs scale, soft and Ductility, malleabl ...
was
cupellation Cupellation is a refining process in metallurgy in which ores or alloyed metals are treated under very high temperatures and subjected to controlled operations to separate noble metals, like gold and silver, from base metals, like lead, co ...
. This process involved melting impure lead samples in a cupel, a small porous container designed for purification that would aid in the oxidation process, while being able to withstand the heat needed to melt these metals in a furnace. This reaction would
oxidize Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
the lead to
litharge Litharge (from Greek , 'stone' + 'silver' ) is one of the natural mineral forms of lead(II) oxide, PbO. Litharge is a secondary mineral which forms from the oxidation of galena ores. It forms as coatings and encrustations with internal tetr ...
, along with any other impurities present, whereas the silver would not get oxidized. In the 18th century, the process was carried on using a kind of
reverberatory furnace A reverberatory furnace is a metallurgy, metallurgical or process Metallurgical furnace, furnace that isolates the material being processed from contact with the fuel, but not from contact with combustion gases. The term ''reverberation'' is use ...
, but differing from the usual kind in that air was blown over the surface of the molten lead from
bellows A bellows or pair of bellows is a device constructed to furnish a strong blast of air. The simplest type consists of a flexible bag comprising a pair of rigid boards with handles joined by flexible leather sides enclosing an approximately airtig ...
or (in the 19th century) blowing cylinders.


Pattinson Process

The Pattinson process was
patent A patent is a type of intellectual property that gives its owner the legal right to exclude others from making, using, or selling an invention for a limited period of time in exchange for publishing an sufficiency of disclosure, enabling discl ...
ed by its inventor, Hugh Lee Pattinson, in 1833 who described it as, "An improved method for separating silver from lead". It exploited the fact that in molten lead (containing traces of silver), the first metal to solidify out of the liquid is lead, leaving the remaining liquid richer in silver. Pattinson's equipment consisted a row of up to 13 iron pots, each heated from below. Some lead, naturally containing a small percentage of silver, was loaded into the central pot and melted. This was then allowed to cool. As the lead solidified it is removed using large, perforated iron ladles and moved to the next pot in one direction, and the remaining metal which was now richer in silver was then transferred to the next pot in the opposite direction. The process was repeated from one pot to the next, the lead accumulating in the pot at one end and metal enriched in silver in the pot at the other.Rowe, 1983. pp 189–190. The level of enrichment possible is limited by the lead-silver eutectic and typically the process stopped around 600 to 700 ounces per ton (approx. 2%), so further separation is carried out by cupellation. The process was economic for lead containing at least 250 grams of silver per ton.Tylecote, 1992. pp. 157–158.


Parkes Process

The
Parkes process The Parkes process is a pyrometallurgical industrial process for removing silver from lead during the production of bullion. It is an example of liquid–liquid extraction. The process takes advantage of two liquid-state properties of zinc. The fi ...
, patented in 1850 by
Alexander Parkes Alexander Parkes (29 December 1813 29 June 1890) was a metallurgist and inventor from Birmingham, England. He created Parkesine, the first man-made plastic. Biography The son of a manufacturer of brass locks, Parkes was apprenticed to Messen ...
, uses molten
zinc Zinc is a chemical element; it has symbol Zn and atomic number 30. It is a slightly brittle metal at room temperature and has a shiny-greyish appearance when oxidation is removed. It is the first element in group 12 (IIB) of the periodic tabl ...
. Zinc is not
miscible Miscibility () is the property of two substances to mix in all proportions (that is, to fully dissolve in each other at any concentration), forming a homogeneous mixture (a solution). Such substances are said to be miscible (etymologically ...
with lead and when the two molten metals are mixed, the zinc separates and floats to the top with ~2% lead. However, silver dissolves more easily in zinc, so the upper layer of zinc carries a significant portion of the silver. The melt is then cooled until the zinc solidifies and the
dross Dross is a mass of solid impurities floating on a molten metal or dispersed in the metal, such as in wrought iron. It forms on the surface of low- melting-point metals such as tin, lead, zinc or aluminium or alloys by oxidation of the metal. Fo ...
is skimmed off. The silver is then recovered by volatilizing the zinc. The Parkes process largely replaced the Pattinson process, except where the lead contained insufficient silver. In such a case, the Pattinson process provided a method to enrich it in silver to about 40 to 60 ounces per ton, at which concentration it could be treated using the Parkes process.


Copper


Fire refining

The initial product of
copper Copper is a chemical element; it has symbol Cu (from Latin ) and atomic number 29. It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. A freshly exposed surface of pure copper has a pinkish-orang ...
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 that is used to obtain many metals such as iron-making, iron, copper extraction, copper ...
was impure "blister" copper, which contained sulfur and oxygen. To remove these impurities, the blister copper was repeatedly melted and solidified, undergoing a cycle of oxidation and reduction. In one of the previous melting stages, lead was added. Gold and silver preferentially dissolved in this, thus providing a means of recovering these precious metals. To produce purer copper suitable for making copper plates or hollow-ware, further melting processes were undertaken, using charcoal as fuel. The repeated application of such fire-refining processes was capable of producing copper that was 98.5-99.5% pure.


Electrolytic refining

The purest copper is obtained by an
electrolytic An electrolyte is a substance that conducts electricity through the movement of ions, but not through the movement of electrons. This includes most soluble salts, acids, and bases, dissolved in a polar solvent like water. Upon dissolving, the ...
process, undertaken using a slab of impure copper as the
anode An anode usually is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, which is usually an electrode of the device through which conventional current leaves the devic ...
and a thin sheet of pure copper as the
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device such as a lead-acid battery. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. Conventional curren ...
. The
electrolyte An electrolyte is a substance that conducts electricity through the movement of ions, but not through the movement of electrons. This includes most soluble Salt (chemistry), salts, acids, and Base (chemistry), bases, dissolved in a polar solven ...
is an acidic solution of copper (II) sulfate. By passing
electricity Electricity is the set of physical phenomena associated with the presence and motion of matter possessing an electric charge. Electricity is related to magnetism, both being part of the phenomenon of electromagnetism, as described by Maxwel ...
through the cell, copper is dissolved from the anode and deposited on the cathode. However, impurities either remain in solution or collect as an insoluble sludge. This process only became possible following the invention of the
dynamo "Dynamo Electric Machine" (end view, partly section, ) A dynamo is an electrical generator that creates direct current using a commutator. Dynamos employed electromagnets for self-starting by using residual magnetic field left in the iron cores ...
; it was first used in South
Wales Wales ( ) is a Countries of the United Kingdom, country that is part of the United Kingdom. It is bordered by the Irish Sea to the north and west, England to the England–Wales border, east, the Bristol Channel to the south, and the Celtic ...
in 1869.


Iron


Wrought iron

The product of the
blast furnace A blast furnace is a type of metallurgical furnace used for smelting to produce industrial metals, generally pig iron, but also others such as lead or copper. ''Blast'' refers to the combustion air being supplied above atmospheric pressure. In a ...
is
pig iron Pig iron, also known as crude iron, is an intermediate good used by the iron industry in the production of steel. It is developed by smelting iron ore in a blast furnace. Pig iron has a high carbon content, typically 3.8–4.7%, along with si ...
, which contains 4–5%
carbon Carbon () is a chemical element; it has chemical symbol, symbol C and atomic number 6. It is nonmetallic and tetravalence, tetravalent—meaning that its atoms are able to form up to four covalent bonds due to its valence shell exhibiting 4 ...
and usually some
silicon Silicon is a chemical element; it has symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic lustre, and is a tetravalent metalloid (sometimes considered a non-metal) and semiconductor. It is a membe ...
. To produce a forgeable product, a further process was needed (usually described as ''fining'', rather than ''refining)''. From the 16th century, this was undertaken in a
finery forge A finery forge is a forge used to produce wrought iron from pig iron by decarburization in a process called "fining" which involved liquifying cast iron in a fining hearth and decarburization, removing carbon from the molten cast iron through Redo ...
. At the end of the 18th century, this began to be replaced by puddling (in a
puddling furnace Puddling is the process of converting pig iron to bar (wrought) iron in a coal fired reverberatory furnace. It was developed in England during the 1780s. The molten pig iron was stirred in a reverberatory furnace, in an Redox, oxidizing enviro ...
), which was in turn gradually superseded by the production of mild steel by the
Bessemer process The Bessemer process was the first inexpensive industrial process for the mass production of steel from molten pig iron before the development of the open hearth furnace. The key principle is steelmaking, removal of impurities and undesired eleme ...
.


Refined iron

The term refining is used in a narrower context.
Henry Cort Henry Cort (c. 1740 – 23 May 1800) was an English ironware producer who was formerly a Navy pay agent. During the Industrial Revolution in England, Cort began refining iron from pig iron to wrought iron (or bar iron) using innovative productio ...
's original puddling process only worked where the raw material was white
cast iron Cast iron is a class of iron–carbon alloys with a carbon content of more than 2% and silicon content around 1–3%. Its usefulness derives from its relatively low melting temperature. The alloying elements determine the form in which its car ...
, rather than the grey
pig iron Pig iron, also known as crude iron, is an intermediate good used by the iron industry in the production of steel. It is developed by smelting iron ore in a blast furnace. Pig iron has a high carbon content, typically 3.8–4.7%, along with si ...
that was the usual raw material for finery forges. To use grey
pig iron Pig iron, also known as crude iron, is an intermediate good used by the iron industry in the production of steel. It is developed by smelting iron ore in a blast furnace. Pig iron has a high carbon content, typically 3.8–4.7%, along with si ...
, a preliminary refining process was necessary to remove silicon. The pig iron was melted in a ''running out furnace'' and then run out into a trough. This process oxidized the silicon to form a slag, which floated on the iron and was removed by lowering a dam at the end of the trough. The product of this process was a white metal, known as ''finers metal'' or ''refined iron''.


Precious metals

Precious metal refining is the separation of
precious metal Precious metals are rare, naturally occurring metallic chemical elements of high Value (economics), economic value. Precious metals, particularly the noble metals, are more corrosion resistant and less reactivity (chemistry), chemically reac ...
s from noble-metalliferous materials. Examples of these materials include used
catalysts Catalysis () is the increase in reaction rate, rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst ...
, electronic assemblies,
ore Ore is natural rock or sediment that contains one or more valuable minerals, typically including metals, concentrated above background levels, and that is economically viable to mine and process. The grade of ore refers to the concentration ...
s, or metal
alloy An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...
s.


Process

In order to isolate noble-metalliferous materials,
pyrolysis Pyrolysis is a process involving the Bond cleavage, separation of covalent bonds in organic matter by thermal decomposition within an Chemically inert, inert environment without oxygen. Etymology The word ''pyrolysis'' is coined from the Gree ...
and/or
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
procedures are used. In pyrolysis, the noble-metalliferous products are released from the other materials by solidifying in a melt to become
cinder Cinder or Cinders may refer to: In general * Ember, also called cinder * Ash, also called cinder * Scoria, or cinder, a type of volcanic rock In computing * Cinder (programming library), a C++ programming library for visualization *Cinder, Ope ...
and then poured off or
oxidized Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
. In hydrolysis, the noble-metalliferous products are dissolved either in
aqua regia Aqua regia (; from Latin, "regal water" or "royal water") is a mixture of nitric acid and hydrochloric acid, optimally in a molar concentration, molar ratio of 1:3. Aqua regia is a fuming liquid. Freshly prepared aqua regia is colorless, but i ...
(consisting of
hydrochloric acid Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
and
nitric acid Nitric acid is an inorganic compound with the formula . It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into nitrogen oxide, oxides of nitrogen. Most com ...
) or in a hydrochloric acid and
chlorine Chlorine is a chemical element; it has Symbol (chemistry), symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between ...
gas in solution. Subsequently, certain metals can be precipitated or reduced directly with a salt, gas, organic, and/or nitro hydrate connection. Afterwards, they go through cleaning stages or are recrystallized. The precious metals are separated from the metal
salt In common usage, salt is a mineral composed primarily of sodium chloride (NaCl). When used in food, especially in granulated form, it is more formally called table salt. In the form of a natural crystalline mineral, salt is also known as r ...
by
calcination Calcination is thermal treatment of a solid chemical compound (e.g. mixed carbonate ores) whereby the compound is raised to high temperature without melting under restricted supply of ambient oxygen (i.e. gaseous O2 fraction of air), generally f ...
. The noble-metalliferous materials are hydrolyzed first and thermally prepared ( pyrolyzed) thereafter. The processes are better yielding when using catalysts that may sometimes contain precious metals themselves. When using catalysts, the recycling product is removed in each case and driven several times through the cycle.


See also

* * *
List of alumina refineries This is a list of alumina Refining (metallurgy), refineries in the world. The list is incomplete and missing some data. Smelter-grade alumina refineries Specialty alumina plants See also *List of aluminium smelters References Sources

...


Bibliography

* J. Day and R. F. Tylecote, ''The Industrial Revolution in Metals'' (The Institute of Metals, London 1991). * Söderberg, A. 2011
Eyvind Skáldaspillir's silver - refining and standards in pre-monetary economies in the light of finds from Sigtuna and Gotland
Situne Dei 2011. Edberg, R. Wikström, A. (eds). Sigtuna. * R. F. Tylecote, ''A history of metallurgy'' (Institute of materials, London 1992).
Newcastle University: Hugh Lee Pattinson


References

{{Authority control Metallurgical processes