PROGRESS IN GOLD REFINING

Fathi Habashi Laval University, Quebec City, Canada Fathi.Habashi@arul.ulaval.ca ABSTRACT World output of gold is about 2800 tonnes usually refined to 99.99+% purity. A combination of pyro-, hydro-, and electrometallurgical processes are used. Because of the high price of the metal large inventories in the plant are not tolerated and a 24-hours processing is usually the norm. Gold with high silver content must be refined by a different method from that with low silver content. The Rand Refinery in South Africa was at one time the largest in the world because the South African gold was about one thousand tonnes per year. A review of refining processes is outlined. INTRODUCTION Refining is a necessary step in treating a metal to decrease its impurities so that it can be used for a variety of purposes [Jones, 1971]. Physical and electrochemical properties of a metal are greatly influenced by the level of impurities. Thus ductility, electrical conductivity, and other properties improve remarkably with increased purity. Refining is, therefore, an important metallurgical operation. New techniques have to be developed for producing pure metals and new methods of analysis have been devised for quality control. Raw gold ingots produced at the mine site or scrap gold are shipped to refiners for obtaining pure ingots by pyro- , hydro- , or electrometallurgical methods [Adamson, 1972]. Silver refining is almost always associated with a gold refinery. Fire assay is still widely used for gold determination in raw ingots [Bugbee, 1940] PYROMETALLURGICAL REFINING Refining of gold bullion by selective oxidation using chlorine gas is known as the Miller Process after its inventor Francis B. Miller (1828-1887), and is used at some mints. In this process the bullion is melted, then poured into heated clay crucibles containing borax, which forms a molten layer on the surface of the bullion. The crucibles, about 20 cm in diameter and 30 cm high, are heated in a furnace (Figure 1). Each crucible is provided with a slotted cover to allow inserting or withdrawing of clay pipes through which chlorine is admitted. As a safeguard against leakage or breakage, each crucible is placed inside a graphite crucible. The base metals are attacked first and volatilize as chlorides. They are collected in a flue dust recovery system. After the base metals have been practically eliminated, silver is attacked next and AgCl (m.p. 455C) floats on the surface of the gold beneath the borax layer. It is skimmed off and collected for silver recovery. Chlorination is complete and the gold is ready for casting when a clay rod held in the fumes forms a brownish stain indicating the formation of gold chloride.

Figure 1 - Miller process for gold refining [Jones, 1972, Habashi, 2002] HYDROMETALLURGICAL REFINING Small scale refining of gold, e.g., in mints, is done by selective leaching. The method used depends on the gold content as well as on the type of impurities present. While silver is soluble in both nitric and sulfuric acids, and gold is insoluble, yet these acids cannot be used to dissolve silver away from an alloy containing more than 25% Au. For high-gold alloys, aqua regia is therefore used. In such alloys, gold is leached, while silver forms an insoluble residue. Table 1 - Summary of gold refining processes by leaching [Habashi, 1999]
( = attacked, x = not attacked)

Alloy

Alloy composition [%] Ag Au 0 25 30 50 75 90 92 100

1 2

Attack by Remarks HNO3 or Aqua H2SO41 regia2

Low-gold bullion

High-gold bullion

100 75 70 50 25 10 8 0

x x x x x x

x x x x x x

Bullion treated by HNO3 or H2SO4. Bullion must be alloyed with Ag before treatment with HNO3 or H2SO4.

Bullion treated by aqua regia.

Ag is soluble but Au is insoluble. Au is soluble but Ag is insoluble due to the formation of AgCl

Gold is soluble in aqua regia, but a goldsilver alloy containing more than 8% Ag cannot be attacked due to the formation of an insoluble layer of AgCl. Therefore, the aqua regia leaching process is used only for refining high-grade bullions, where the silver does not amount to more than 8%, or to cases where the bullion contains enough copper to open it up to attack in spite of the silver present. A summary of these processes is shown in Table 1. In both cases, the bullion is first melted and poured in water to obtain granules suitable for leaching.

Low-gold alloys
In such alloys, silver is selectively leached. It is necessary to alloy the bullion with silver such that silver constitutes 75% of the alloy. Such an alloy is known as parting alloy. In the nitric acid process (Figure 2), the reactions are: 3Ag + 4HNO3 3AgNO3 + 2H2O + NO 3Cu + 8HNO3 3Cu(NO3)2 + 4H2O + 2NO
HNO3 AuAg parting alloy

Leaching Water Filtration NaCl Precipitation of AgCl Fe Cementation Washing Drying melting casting Gold

Au residue

Figure 2 - Nitric acid process for refining gold The reaction is carried out in stainless steel vessels, and nitric gases are oxidized and recovered as HNO3. Silver and platinum will go into solution, while Au, Ru, Rh, and Ir are left behind as a finely divided black mud. Silver is recovered from the solution by precipitation as AgCl by adding NaCl. Silver chloride is then converted to metallic silver by contact with scrap iron. The gold residue is then washed, dried, melted, and cast. The introduction of sulfuric acid as a leaching agent for refining gold reduced the cost greatly as compared with the nitric acid process. Cast iron vessels could be used, and copper in the bullion is converted to copper sulfate, which is a marketable product. The process is shown in Figure 3 and the reactions are: 2Ag + 2H2SO4 Ag2SO4 + 2H2O + SO2 Cu + 2H2SO4 CuSO4 + 2H2O + SO2

Silver

H2SO4

AuAg parting alloy

Leaching Solids Siphoning

Water Washing Solution to waste Fe Solids Silver

Ag2SO4

Drying melting casting

Gold

Crystallization

Filtration

Crystallization

Filtration

CuSO4 5H2O

Figure 3 - Sulfuric acid process for refining gold Silver, copper, and part of the palladium are dissolved, while Au, Pt, Ru, Rh, and Ir are not. The gold residue is separated, washed, dried, briquetted, melted, and cast. The solution containing silver and copper is transferred to lead-lined tanks, diluted with water, and cooled to crystallize Ag2SO4. Silver sulfate is slightly soluble in cold water but dissolves readily in hot concentrated H2SO4. The crystals are separated, washed, reduced with scrap iron, melted, and cast. The mother liquor is evaporated and cooled to crystallize and separate CuSO4. The residual sulfuric acid is recycled. This process cannot be used for bullions containing appreciable quantities of lead, because PbSO4 will be left behind with the gold residue and considerable fluxing of the final product would be necessary to remove it.

High-gold alloys
As indicated earlier, aqua regia is used to attack high-gold alloys since both nitric and sulfuric acids are not effective. In this method, gold, copper, and other impurities go into solution while silver remains behind as silver chloride. The leaching equations are: 2Au + 3Cl2 2AuCl3 (soluble) 2Ag + Cl2 2AgCl (insoluble) Cu + Cl2 CuCl2 (soluble) The dissolving pans are made of stoneware, glass, or fused silica and have a capacity of about 250 liters. Each pan is filled two-thirds with HCl and heated by steam injection. The nitric acid is added at intervals to maintain a vigorous reaction. The dissolution of gold follows the equation: 4HCl + HNO3 + Au HAuCl4 + NO + 2H2O When the process is complete, the excess acid is boiled off: HNO3 + 3HCl NOCl + 2H2O + Cl2 The liquor is allowed to settle, and the supernatant solution is siphoned and treated with a reducing agent (e.g., FeCl2, oxalic acid, SO2) to precipitate gold, which is filtered off, washed, and melted (Figure 4). Silver chloride residues are washed with water, and the first washings (containing gold) are returned to the dissolving pan. The material is then reduced with scrap iron to metallic silver.

Aqua regia AuAg bullion (Ag < 8%) Leaching

Boiling Solids Settling AgCl

Water Washing

Fe Silver Cementation

Reduction

Water Washing Drying melting casting Gold

Filtration Solution to waste

Figure 4 -Aqua regia process for refining high-gold bullions This process is of special value when refining platiniferous gold. Platinum and palladium are dissolved together with gold, while Rh, Ru, and Ir remain with the silver chloride. Gold is precipitated by FeCl2, and then filtered, and Pt and Pd are recovered from the solution by the usual methods. Solvent extraction of gold Gold can be extracted from chloride solutions by a number of organic solvents. According to Martnez et al. (1999) gold (III) is extracted from hydrochloric acid by the chloride salt of the amine Hostarex A327 in n-decane according to:

Other solvents were also proposed by Barroso et al. in 1997. The Harmony Refinery, situated at Harmony Gold Mine in the Free State Goldfields of South Africa operated a solvent extraction process for gold refining. A sludge containing between 50 and 85% gold was solubilized by leaching for 2 hours in hydrochloric acid under chlorine gas stream [Finkelstein et al., 1966] (Figure 5). The bulk of the base metals and platinum group metals are also solubilized under these conditions. Silver precipitates as silver chloride and is collected as a solid residue along with any silica. This material can be treated in a separate processing step to recover residual gold and purify the silver.

Figure 5 - Refining of gold by solvent extraction [Feather et al., 1997, Sole et al., 1998]

The leach solution, containing about 65 g/L gold, is treated by solvent extraction [the organic solvent was not specified]. Gold is selectively extracted into the organic phase, while all other metal ions report to the rafinate. Small quantities of co-extracted impurities are scrubbed from the loaded organic phase before it is stripped to produce a purified, concentrated gold solution. The stripped organic phase is then recycled to the extraction circuit. The HCI-rich rafinate from the extraction section is returned to the leach, with a small bleed to control the build up of base-metal impurities in the leach/solvent extraction circuit. Table 2 - Typical compositions of leach solution and loaded strip solution

Gold is recovered as a metal powder by direct reduction from the loaded strip liquor. Use of gaseous sulfur dioxide as the reducing agent produces gold meeting the specification of 99.99% purity. The leach and reduction are operated batchwise, while the solvent extraction is a continuous operation. Equipment is mainly made of fiber-reinforced plastic, polypropylene, and high-density polyethylene. ELECTROMETALLURGICAL REFINING In electrorefining technology the impure metal is cast in form of anode, then dissolved electrolytically: M Mn+ + ne The metal ion liberated at the anode migrates towards the cathode and deposits on its surface. The anodes cannot be dissolved completely, and between 10% and 30% of its weight remains at the end of the cycle as anode scrap. The scrap is recycled. When soluble impurities can co-deposit onto the cathode together with the metal to be refined, then the cathodes are placed in diaphragmequipped boxes. The impure anolyte is withdrawn from the common anode compartment, purified and returned to the cathode boxes. Energy consumption is low because the anodic reaction is the same as the cathodic. The electrometallurgical route is conducted in Wohlwill cell (Figures 6 and 7) named after its German inventor Emil Wohlwill. Feed material is usually the anode slimes from silver refining. These are collected, purified to remove silver, and cast as anodes containing approximately 94% Au, 5% Ag, and 1% Cu, Pt, Pb, and Pd and measuring about 20 x 10 x 1 cm. Electrolysis is

carried out in acidic chloride solutions containing 150200 g/L Au and 140 g/L HCl at about 70C and at a current density of 1 200 A/m2, using thin gold ribbon cathodes. At the anode, the reaction Au + 4Cl [AuCl4] + 3e

Figure 6 - Electrorefining of gold in Wohlwill cell [Habashi, 1998]

Figure 7 - Electrorefined gold being removed from cell [Habashi, 1998]

takes place, and at the cathode the reverse reaction. Anodes and cathodes are normally replaced every two days. During electrolysis impurities go into solution, silver precipitates as silver chloride, and pure gold deposits on the cathode. These are lifted out of the solution periodically to remove the nodules and thereby prevent short-circuiting between cathode and anode. Electrolyte is replaced periodically when the total concentration of platinum and palladium in the electrolyte exceeds about 75 g/L. Some gold is present in the silver chloride slimes due to the disproportionation of monovalent gold in solution: 3Au+ 2Au + Au3+ The electrolyte from the gold refining process contains Pt, Pd, etc. These metals are recovered by precipitation as (NH4)2PtCl6 and (NH4)2PdCl6 then decomposition to sponge metal. High-purity gold 99.999% is obtained by melting and casting the cathodes in form of anodes and repeating the process. The advantage of the process is the high purity of the gold produced usually 99.9%. In addition, the by-products, especially platinum-group metals, are also relatively easy to isolate. A disadvantage is the fairly long period during which the noble metal is tied up, leading to considerable financial losses.

SILVER
Silver is usually the major impurity in gold and most gold refineries have a silver refining unit. Electrolysis is carried out in silver nitratesodium nitratenitric acid electrolyte containing 150 g/L Ag (pH 11.5) at a current density of ca. 300 A/m2 and a temperature of ca. 35C. Pure silver

deposits on the cathode while gold and platinum remain insoluble and are collected in the slimes. Copper, lead, and palladium accumulate in solution. When the copper or lead content in the electrolyte exceeds ca. 10 g/L, or the palladium content exceeds ca. 1 g/L, the solution is removed, de-silverized, and discarded, and new electrolyte is made by dissolving scrap anodes in hot nitric acid. Silver deposited in a loose crystalline form (Figure 8) is collected, melted, and cast as 1 000-oz bars of 99.99% purity. Higher purity of 99.999% is obtained by double electrolysis. Electrolysis is usually conducted for two days and the residual anodes are 5 to 5% of the original. Two types of cells are used:

Figure 8 - Silver crystals obtained by electrolysis (enlarged)

ThumBalbach cell
These cells are mainly used in North America. They consist of shallow tanks equipped with graphite or stainless steel bottoms acting as cathodes. The anodes are arranged horizontally above the cathodes, resting on wooden frames with canvas bags to retain the slimes (Figures 9 and 10). Each cell is provided with only one anode and one cathode. The cathode is a stainless steel plate covering the entire floor area. Above this, at a distance of 10 cm, is a slightly smaller framework of nonconducting material, covered with fabric and containing the anode. The crude silver anodes are completely covered by electrolyte. An advantage of this cell is that the anode slime is recovered easily. Disadvantages include the large space requirement and high energy consumption.
+ Anode basket Silver anodes Anodic slimes Silver crystals Cathode

Anode bag Electrolyte

Figure 9 - ThumBalbach cell

Figure 10 - ThumBalbach silver electrorefining plant

Moebius cell
These cells are mainly used in Europe. In these cells the anodes and the stainless steel cathodes are arranged vertically (Figures 11 and 12). Each anode is encased in a polypropylene or canvas bag which collects the slimes. Electrolyte mixing is accomplished by an oscillating cathode scraper which also brushes the silver crystals off the cathode plates. The crystals are collected in a removable basket with a filter cloth bottom, which is situated beneath the electrode. The cell voltage is 2.02.5 V and the energy consumption is about 0.6 kWh/kg of silver.
Silver anodes + + Cathodes

Electrolyte Me chanical scraper

Anode bag

Silver crystals

Figure 11 - Mbius cell

Figure 12 - Mbius plant for silver electrorefining The spent anodes are replaced continually by new anodes, so that interruption of electrolysis is necessary only if the electrolyte must be replaced due to excessive copper concentration, or if the anode bags have to be emptied. The electrolyte is usually treated with copper to recover the silver by cementation, and the copper is then recovered by cementation with iron. The process is most suitable for crude silver containing > 90% Ag. With high copper content, the electrolyte must be regenerated too often, and with high gold content, the anode bags require frequent emptying. Both are costly operations. A single electrolysis gives a purity of 99.95 99.99% Ag and a double electrolysis gives a purity of 99.99599.999%. SUGGESTED READING R.J. Adamson, editor, Gold Metallurgy in South Africa, Chamber of Mines of South Africa, Johannesburg 1972 M. A. Barroso, F. A. Lpez, A. Sastre, F. J. Alguacil, Study of the Extraction of Gold(III) in Aqueous Hydrochloric acid Media by the Phosphine Oxide Cyanex 925, Hydrometallurgy 45(1), 199-209 (1997) E. E. Bugbee, A Textbook of Fire Assaying, Wiley, New York 1940 A. Feather, K.C. Sole, and L.J. Bryson, Gold Refining by Solvent Extractionthe Minataur Process, Journal of The South African Institute of Mining and Metallurgy 169-173 (1997) N. P. Finkelstein, R. M. Hoare, G. S. James, D. D. Howat, "An Aqueous Chlorination Process for the Treatment of Merrill Slimes and Gravity Concentrates from Gold Ores. Part I. A Study of the Chemistry of the Process and a Report of Laboratory Testwork," Journal of the South African lnstitute of Mining and Metallurgy, 66 (12), 196-215 (1966) F. Habashi, Principles of Extractive Metallurgy, Volume 4 - Amalgam & Electrometallurgy, Mtallurgie Extractive Qubec, Qubec City, Canada 1998. Distributed by Laval University Bookstore. www.zone.ul.ca

F. Habashi, Textbook of Hydrometallurgy, Mtallurgie Extractive Qubec, Qubec City, Canada 1993, second edition 1999. Distributed by Laval University Bookstore. www.zone.ul.ca F. Habashi, Textbook of Pyrometallurgy, Mtallurgie Extractive Qubec, Qubec City, Canada 2002. Distributed by Laval University Bookstore. www.zone.ul.ca M.J. Jones (editor), Advances in Extractive Metallurgy and Refining, Institution of Mining & Metallurgy, London 1972 S. Martnez, A.M. Sastre, and F.J. Alguacil Solvent Extraction of Gold (III) by the Chloride Salt of the Tertiaryamine Hostarex A327. Estimation of the interaction coefficient between AuCl4 and H+ , Hydrometallurgy 52(1), 6370 (1999) K.C. Sole et al., Commercialisation of the Minataur Rocess: Commissioning of Harmony Gold Refinery, pp. 175-186 in EPD Congress 1998, edited by B. Mihra, The Minerals, Metals & Materials Society, Denver, Colorado 1998